The math behind the maser

As I skipped the mathematical arguments in my previous post so as to focus on the essential results only, I thought it would be good to complement that post by looking at the math once again, so as to ensure we understand what it is that we’re doing. So let’s do that now. We start with the easy situation: free space.

The two-state system in free space

We started with an ammonia molecule in free space, i.e. we assumed there were no external force fields, like a gravitational or an electromagnetic force field. Hence, the picture was as simple as the one below: the nitrogen atom could be ‘up’ or ‘down’ with regard to its spin around its axis of symmetry.

Capture

It’s important to note that this ‘up’ or ‘down’ direction is defined in regard to the molecule itself, i.e. not in regard to some external reference frame. In other words, the reference frame is that of the molecule itself. For example, if I flip the illustration above – like below – then we’re still talking the same states, i.e. the molecule is still in state 1 in the image on the left-hand side and it’s still in state 2 in the image on the right-hand side. 

Capture

We then modeled the uncertainty about its state by associating two different energy levels with the molecule: E0 + A and E− A. The idea is that the nitrogen atom needs to tunnel through a potential barrier to get to the other side of the plane of the hydrogens, and that requires energy. At the same time, we’ll show the two energy levels are effectively associated with an ‘up’ or ‘down’ direction of the electric dipole moment of the molecule. So that resembles the two spin states of an electron, which we associated with the +ħ/2 and −ħ/2 energies respectively. So if E0 would be zero (we can always take another reference point, remember?), then we’ve got the same thing: two energy levels that are separated by some definite amount: that amount is 2A for the ammonia molecule, and ħ when we’re talking quantum-mechanical spin. I should make a last note here, before I move on: note that these energies only make sense in the presence of some external field, because the + and − signs in the E0 + A and E− A and +ħ/2 and −ħ/2 expressions make sense only with regard to some external direction defining what’s ‘up’ and what’s ‘down’ really. But I am getting ahead of myself here. Let’s go back to free space: no external fields, so what’s ‘up’ or ‘down’ is completely random here. 🙂

Now, we also know an energy level can be associated with a complex-valued wavefunction, or an amplitude as we call it. To be precise, we can associate it with the generic a·e−(i/ħ)·(E·t − px) expression which you know so well by now. Of course,  as the reference frame is that of the molecule itself, its momentum is zero, so the px term in the a·e−(i/ħ)·(E·t − px) expression vanishes and the wavefunction reduces to a·ei·ω·t a·e−(i/ħ)·E·t, with ω = E/ħ. In other words, the energy level determines the temporal frequency, or the temporal variation (as opposed to the spatial frequency or variation), of the amplitude.

We then had to find the amplitudes C1(t) = 〈 1 | ψ 〉 and C2(t) =〈 2 | ψ 〉, so that’s the amplitude to be in state 1 or state 2 respectively. In my post on the Hamiltonian, I explained why the dynamics of a situation like this can be represented by the following set of differential equations:

Hamiltonian

As mentioned, the Cand C2 functions evolve in time, and so we should write them as C= C1(t) and C= C2(t) respectively. In fact, our Hamiltonian coefficients may also evolve in time, which is why it may be very difficult to solve those differential equations! However, as I’ll show below, one usually assumes they are constant, and then one makes informed guesses about them so as to find a solution that makes sense.

Now, I should remind you here of something you surely know: if Cand Care solutions to this set of differential equations, then the superposition principle tells us that any linear combination a·C1 + b·Cwill also be a solution. So we need one or more extra conditions, usually some starting condition, which we can combine with a normalization condition, so we can get some unique solution that makes sense.

The Hij coefficients are referred to as Hamiltonian coefficients and, as shown in the mentioned post, the H11 and H22 coefficients are related to the amplitude of the molecule staying in state 1 and state 2 respectively, while the H12 and H21 coefficients are related to the amplitude of the molecule going from state 1 to state 2 and vice versa. Because of the perfect symmetry of the situation here, it’s easy to see that H11 should equal H22 , and that H12 and H21 should also be equal to each other. Indeed, Nature doesn’t care what we call state 1 or 2 here: as mentioned above, we did not define the ‘up’ and ‘down’ direction with respect to some external direction in space, so the molecule can have any orientation and, hence, switching the i an j indices should not make any difference. So that’s one clue, at least, that we can use to solve those equations: the perfect symmetry of the situation and, hence, the perfect symmetry of the Hamiltonian coefficients—in this case, at least!

The other clue is to think about the solution if we’d not have two states but one state only. In that case, we’d need to solve iħ·[dC1(t)/dt] = H11·C1(t). That’s simple enough, because you’ll remember that the exponential function is its own derivative. To be precise, we write: d(a·eiωt)/dt = a·d(eiωt)/dt = a·iω·eiωt, and please note that can be any complex number: we’re not necessarily talking a real number here! In fact, we’re likely to talk complex coefficients, and we multiply with some other complex number (iω) anyway here! So if we write iħ·[dC1/dt] = H11·C1 as dC1/dt = −(i/ħ)·H11·C1 (remember: i−1 = 1/i = −i), then it’s easy to see that the Ca·e–(i/ħ)·H11·t function is the general solution for this differential equation. Let me write it out for you, just to make sure:

dC1/dt = d[a·e–(i/ħ)H11t]/dt = a·d[e–(i/ħ)H11t]/dt = –a·(i/ħ)·H11·e–(i/ħ)H11t

= –(i/ħ)·H11·a·e–(i/ħ)H11= −(i/ħ)·H11·C1

Of course, that reminds us of our generic wavefunction a·e−(i/ħ)·E0·t wavefunction: we only need to equate H11 with E0 and we’re done! Hence, in a one-state system, the Hamiltonian coefficient is, quite simply, equal to the energy of the system. In fact, that’s a result can be generalized, as we’ll see below, and so that’s why Feynman says the Hamiltonian ought to be called the energy matrix.

In fact, we actually may have two states that are entirely uncoupled, i.e. a system in which there is no dependence of C1 on Cand vice versa. In that case, the two equations reduce to:

iħ·[dC1/dt] = H11·C1 and iħ·[dC2/dt] = H22·C2

These do not form a coupled system and, hence, their solutions are independent:

C1(t) = a·e–(i/ħ)·H11·t and C2(t) = b·e–(i/ħ)·H22·t 

The symmetry of the situation suggests we should equate a and b, and then the normalization condition says that the probabilities have to add up to one, so |C1(t)|+ |C2(t)|= 1, so we’ll find that = 1/√2.

OK. That’s simple enough, and this story has become quite long, so we should wrap it up. The two ‘clues’ – about symmetry and about the Hamiltonian coefficients being energy levels – lead Feynman to suggest that the Hamiltonian matrix for this particular case should be equal to:

H-matrix

Why? Well… It’s just one of Feynman’s clever guesses, and it yields probability functions that makes sense, i.e. they actually describe something real. That’s all. 🙂 I am only half-joking, because it’s a trial-and-error process indeed and, as I’ll explain in a separate section in this post, one needs to be aware of the various approximations involved when doing this stuff. So let’s be explicit about the reasoning here:

  1. We know that H11 = H22 = Eif the two states would be identical. In other words, if we’d have only one state, rather than two – i.e. if H12 and H21 would be zero – then we’d just plug that in. So that’s what Feynman does. So that’s what we do here too! 🙂
  2. However, H12 and H21 are not zero, of course, and so assume there’s some amplitude to go from one position to the other by tunneling through the energy barrier and flipping to the other side. Now, we need to assign some value to that amplitude and so we’ll just assume that the energy that’s needed for the nitrogen atom to tunnel through the energy barrier and flip to the other side is equal to A. So we equate H12 and H21 with −A.

Of course, you’ll wonder: why minus A? Why wouldn’t we try H12 = H21 = A? Well… I could say that a particle usually loses potential energy as it moves from one place to another, but… Well… Think about it. Once it’s through, it’s through, isn’t it? And so then the energy is just Eagain. Indeed, if there’s no external field, the + or − sign is quite arbitrary. So what do we choose? The answer is: when considering our molecule in free space, it doesn’t matter. Using +A or −A yields the same probabilities. Indeed, let me give you the amplitudes we get for H11 = H22 = Eand H12 and H21 = −A:

  1. C1(t) = 〈 1 | ψ 〉 = (1/2)·e(i/ħ)·(E− A)·t + (1/2)·e(i/ħ)·(E+ A)·t = e(i/ħ)·E0·t·cos[(A/ħ)·t]
  2. C2(t) = 〈 2 | ψ 〉 = (1/2)·e(i/ħ)·(E− A)·t – (1/2)·e(i/ħ)·(E+ A)·t = i·e(i/ħ)·E0·t·sin[(A/ħ)·t]

[In case you wonder how we go from those exponentials to a simple sine and cosine factor, remember that the sum of complex conjugates, i.e eiθ eiθ reduces to 2·cosθ, while eiθ − eiθ reduces to 2·i·sinθ.]

Now, it’s easy to see that, if we’d have used +A rather than −A, we would have gotten something very similar:

  • C1(t) = 〈 1 | ψ 〉 = (1/2)·e(i/ħ)·(E+ A)·t + (1/2)·e(i/ħ)·(E− A)·t = e(i/ħ)·E0·t·cos[(A/ħ)·t]
  • C2(t) = 〈 2 | ψ 〉 = (1/2)·e(i/ħ)·(E+ A)·t – (1/2)·e(i/ħ)·(E− A)·t = −i·e(i/ħ)·E0·t·sin[(A/ħ)·t]

So we get a minus sign in front of our C2(t) function, because cos(α) = cos(–α) but sin(α) = −sin(α). However, the associated probabilities are exactly the same. For both, we get the same P1(t) and P2(t) functions:

  • P1(t) = |C1(t)|2 = cos2[(A/ħ)·t]
  • P2(t) = |C2(t)|= sin2[(A/ħ)·t]

[Remember: the absolute square of and −is |i|= +√12 = +1 and |i|2 = (−1)2|i|= +1 respectively, so the i and −i in the two C2(t) formulas disappear.]

You’ll remember the graph:

graph

Of course, you’ll say: that plus or minus sign in front of C2(t) should matter somehow, doesn’t it? Well… Think about it. Taking the absolute square of some complex number – or some complex function , in this case! – amounts to multiplying it with its complex conjugate. Because the complex conjugate of a product is the product of the complex conjugates, it’s easy to see what happens: the e(i/ħ)·E0·t factor in C1(t) = e(i/ħ)·E0·t·cos[(A/ħ)·t] and C2(t) = ±i·e(i/ħ)·E0·t·sin[(A/ħ)·t] gets multiplied by e+(i/ħ)·E0·t and, hence, doesn’t matter: e(i/ħ)·E0·t·e+(i/ħ)·E0·t = e0 = 1. The cosine factor in C1(t) = e(i/ħ)·E0·t·cos[(A/ħ)·t] is real, and so its complex conjugate is the same. Now, the ±i·sin[(A/ħ)·t] factor in C2(t) = ±i·e(i/ħ)·E0·t·sin[(A/ħ)·t] is a pure imaginary number, and so its complex conjugate is its opposite. For some reason, we’ll find similar solutions for all of the situations we’ll describe below: the factor determining the probability will either be real or, else, a pure imaginary number. Hence, from a math point of view, it really doesn’t matter if we take +A or −A for  or  real factor for those H12 and H21 coefficients. We just need to be consistent in our choice, and I must assume that, in order to be consistent, Feynman likes to think of our nitrogen atom borrowing some energy from the system and, hence, temporarily reducing its energy by an amount that’s equal to −A. If you have a better interpretation, please do let me know! 🙂

OK. We’re done with this section… Except… Well… I have to show you how we got those C1(t) and C1(t) functions, no? Let me copy Feynman here:

solutionNote that the ‘trick’ involving the addition and subtraction of the differential equations is a trick we’ll use quite often, so please do have a look at it. As for the value of the a and b coefficients – which, as you can see, we’ve equated to 1 in our solutions for C1(t) and C1(t) – we get those because of the following starting condition: we assume that at t = 0, the molecule will be in state 1. Hence, we assume C1(0) = 1 and C2(0) = 0. In other words: we assume that we start out on that P1(t) curve in that graph with the probability functions above, so the C1(0) = 1 and C2(0) = 0 starting condition is equivalent to P1(0) = 1 and P1(0) = 0. Plugging that in gives us a/2 + b/2 = 1 and a/2 − b/2 = 0, which is possible only if a = b = 1.

Of course, you’ll say: what if we’d choose to start out with state 2, so our starting condition is P1(0) = 0 and P1(0) = 1? Then a = 1 and b = −1, and we get the solution we got when equating H12 and H21 with +A, rather than with −A. So you can think about that symmetry once again: when we’re in free space, then it’s quite arbitrary what we call ‘up’ or ‘down’.

So… Well… That’s all great. I should, perhaps, just add one more note, and that’s on that A/ħ value. We calculated it in the previous post, because we wanted to actually calculate the period of those P1(t) and P2(t) functions. Because we’re talking the square of a cosine and a sine respectively, the period is equal to π, rather than 2π, so we wrote: (A/ħ)·T = π ⇔ T = π·ħ/A. Now, the separation between the two energy levels E+ A and E− A, so that’s 2A, has been measured as being equal, more or less, to 2A ≈ 10−4 eV.

How does one measure that? As mentioned above, I’ll show you, in a moment, that, when applying some external field, the plus and minus sign do matter, and the separation between those two energy levels E+ A and E− A will effectively represent something physical. More in particular, we’ll have transitions from one energy level to another and that corresponds to electromagnetic radiation being emitted or absorbed, and so there’s a relation between the energy and the frequency of that radiation. To be precise, we can write 2A = h·f0. The frequency of the radiation that’s being absorbed or emitted is 23.79 GHz, which corresponds to microwave radiation with a wavelength of λ = c/f0 = 1.26 cm. Hence, 2·A ≈ 25×109 Hz times 4×10−15 eV·s = 10−4 eV, indeed, and, therefore, we can write: T = π·ħ/A ≈ 3.14 × 6.6×10−16 eV·s divided by 0.5×10−4 eV, so that’s 40×10−12 seconds = 40 picoseconds. That’s 40 trillionths of a seconds. So that’s very short, and surely much shorter than the time that’s associated with, say, a freely emitting sodium atom, which is of the order of 3.2×10−8 seconds. You may think that makes sense, because the photon energy is so much lower: a sodium light photon is associated with an energy equal to E = h·f = 500×1012 Hz times 4×10−15  eV·s = 2 eV, so that’s 20,000 times 10−4 eV.

There’s a funny thing, however. An oscillation of a frequency of 500 tera-hertz that lasts 3.2×10−8 seconds is equivalent to 500×1012 Hz times 3.2×10−8 s ≈ 16 million cycles. However, an oscillation of a frequency of 23.97 giga-hertz that only lasts 40×10−12 seconds is equivalent to 23.97×109 Hz times 40×10−12 s ≈ 1000×10−3 = 1 ! One cycle only? We’re surely not talking resonance here!

So… Well… I am just flagging it here. We’ll have to do some more thinking about that later. [I’ve added an addendum that may or may not help us in this regard. :-)]

The two-state system in a field

As mentioned above, when there is no external force field, we define the ‘up’ or ‘down’ direction of the nitrogen atom was defined with regard to its its spin around its axis of symmetry, so with regard to the molecule itself. However, when we apply an external electromagnetic field, as shown below, we do have some external reference frame.

Now, the external reference frame – i.e. the physics of the situation, really – may make it more convenient to define the whole system using another set of base states, which we’ll refer to as I and II, rather than 1 and 2. Indeed, you’ve seen the picture below: it shows a state selector, or a filter as we called it. In this case, there’s a filtering according to whether our ammonia molecule is in state I or, alternatively, state II. It’s like a Stern-Gerlach apparatus splitting an electron beam according to the spin state of the electrons, which is ‘up’ or ‘down’ too, but in a totally different way than our ammonia molecule. Indeed, the ‘up’ and ‘down’ spin of an electron has to do with its magnetic moment and its angular momentum. However, there are a lot of similarities here, and so you may want to compare the two situations indeed, i.e. the electron beam in an inhomogeneous magnetic field versus the ammonia beam in an inhomogeneous electric field.

electric field

Now, when reading Feynman, as he walks us through the relevant Lecture on all of this, you get the impression that it’s the I and II states only that have some kind of physical or geometric interpretation. That’s not the case. Of course, the diagram of the state selector above makes it very obvious that these new I and II base states make very much sense in regard to the orientation of the field, i.e. with regard to external space, rather than with respect to the position of our nitrogen atom vis-á-vis the hydrogens. But… Well… Look at the image below: the direction of the field (which we denote by ε because we’ve been using the E for energy) obviously matters when defining the old ‘up’ and ‘down’ states of our nitrogen atom too!

In other words, our previous | 1 〉 and | 2 〉 base states acquire a new meaning too: it obviously matters whether or not the electric dipole moment of the molecule is in the same or, conversely, in the opposite direction of the field. To be precise, the presence of the electromagnetic field suddenly gives the energy levels that we’d associate with these two states a very different physical interpretation.

ammonia

Indeed, from the illustration above, it’s easy to see that the electric dipole moment of this particular molecule in state 1 is in the opposite direction and, therefore, temporarily ignoring the amplitude to flip over (so we do not think of A for just a brief little moment), the energy that we’d associate with state 1 would be equal to E+ με. Likewise, the energy we’d associate with state 2 is equal to E− με.  Indeed, you’ll remember that the (potential) energy of an electric dipole is equal to the vector dot product of the electric dipole moment μ and the field vector ε, but with a minus sign in front so as to get the sign for the energy righ. So the energy is equal to −μ·ε = −|μ|·|ε|·cosθ, with θ the angle between both vectors. Now, the illustration above makes it clear that state 1 and 2 are defined for θ = π and θ = 0 respectively. [And, yes! Please do note that state 1 is the highest energy level, because it’s associated with the highest potential energy: the electric dipole moment μ of our ammonia molecule will – obviously! – want to align itself with the electric field ε ! Just think of what it would imply to turn the molecule in the field!]

Therefore, using the same hunches as the ones we used in the free space example, Feynman suggests that, when some external electric field is involved, we should use the following Hamiltonian matrix:

H-matrix 2

So we’ll need to solve a similar set of differential equations with this Hamiltonian now. We’ll do that later and, as mentioned above, it will be more convenient to switch to another set of base states, or another ‘representation’ as it’s referred to. But… Well… Let’s not get too much ahead of ourselves: I’ll say something about that before we’ll start solving the thing, but let’s first look at that Hamiltonian once more.

When I say that Feynman uses the same clues here, then… Well.. That’s true and not true. You should note that the diagonal elements in the Hamiltonian above are not the same: E+ με ≠ E+ με. So we’ve lost that symmetry of free space which, from a math point of view, was reflected in those identical H11 = H22 = Ecoefficients.

That should be obvious from what I write above: state 1 and state 2 are no longer those 1 and 2 states we described when looking at the molecule in free space. Indeed, the | 1 〉 and | 2 〉 states are still ‘up’ or ‘down’, but the illustration above also makes it clear we’re defining state 1 and state 2 not only with respect to the molecule’s spin around its own axis of symmetry but also vis-á-vis some direction in space. To be precise, we’re defining state 1 and state 2 here with respect to the direction of the electric field ε. Now that makes a really big difference in terms of interpreting what’s going on.

In fact, the ‘splitting’ of the energy levels because of that amplitude A is now something physical too, i.e. something that goes beyond just modeling the uncertainty involved. In fact, we’ll find it convenient to distinguish two new energy levels, which we’ll write as E= E+ A and EII = E− A respectively. They are, of course, related to those new base states | I 〉 and | II 〉 that we’ll want to use. So the E+ A and E− A energy levels themselves will acquire some physical meaning, and especially the separation between them, i.e. the value of 2A. Indeed, E= E+ A and EII = E− A will effectively represent an ‘upper’ and a ‘lower’ energy level respectively.

But, again, I am getting ahead of myself. Let’s first, as part of working towards a solution for our equations, look at what happens if and when we’d switch to another representation indeed.

Switching to another representation

Let me remind you of what I wrote in my post on quantum math in this regard. The actual state of our ammonia molecule – or any quantum-mechanical system really – is always to be described in terms of a set of base states. For example, if we have two possible base states only, we’ll write:

| φ 〉 = | 1 〉 C1 + | 2 〉 C2

You’ll say: why? Our molecule is obviously always in either state 1 or state 2, isn’t it? Well… Yes and no. That’s the mystery of quantum mechanics: it is and it isn’t. As long as we don’t measure it, there is an amplitude for it to be in state 1 and an amplitude for it to be in state 2. So we can only make sense of its state by actually calculating 〈 1 | φ 〉 and 〈 2 | φ 〉 which, unsurprisingly are equal to 〈 1 | φ 〉 = 〈 1 | 1 〉 C1 + 〈 1 | 2 〉 C2  = C1(t) and 〈 2 | φ 〉 = 〈 2 | 1 〉 C1 + 〈 2 | 2 〉 C2  = C2(t) respectively, and so these two functions give us the probabilities P1(t) and  P2(t) respectively. So that’s Schrödinger’s cat really: the cat is dead or alive, but we don’t know until we open the box, and we only have a probability function – so we can say that it’s probably dead or probably alive, depending on the odds – as long as we do not open the box. It’s as simple as that.

Now, the ‘dead’ and ‘alive’ condition are, obviously, the ‘base states’ in Schrödinger’s rather famous example, and we can write them as | DEAD 〉 and | ALIVE 〉 you’d agree it would be difficult to find another representation. For example, it doesn’t make much sense to say that we’ve rotated the two base states over 90 degrees and we now have two new states equal to (1/√2)·| DEAD 〉 – (1/√2)·| ALIVE 〉 and (1/√2)·| DEAD 〉 + (1/√2)·| ALIVE 〉 respectively. There’s no direction in space in regard to which we’re defining those two base states: dead is dead, and alive is alive.

The situation really resembles our ammonia molecule in free space: there’s no external reference against which to define the base states. However, as soon as some external field is involved, we do have a direction in space and, as mentioned above, our base states are now defined with respect to a particular orientation in space. That implies two things. The first is that we should no longer say that our molecule will always be in either state 1 or state 2. There’s no reason for it to be perfectly aligned with or against the field. Its orientation can be anything really, and so its state is likely to be some combination of those two pure base states | 1 〉 and | 2 〉.

The second thing is that we may choose another set of base states, and specify the very same state in terms of the new base states. So, assuming we choose some other set of base states | I 〉 and | II 〉, we can write the very same state | φ 〉 = | 1 〉 C1 + | 2 〉 Cas:

| φ 〉 = | I 〉 CI + | II 〉 CII

It’s really like what you learned about vectors in high school: one can go from one set of base vectors to another by a transformation, such as, for example, a rotation, or a translation. It’s just that, just like in high school, we need some direction in regard to which we define our rotation or our translation.

For state vectors, I showed how a rotation of base states worked in one of my posts on two-state systems. To be specific, we had the following relation between the two representations:

matrix

The (1/√2) factor is there because of the normalization condition, and the two-by-two matrix equals the transformation matrix for a rotation of a state filtering apparatus about the y-axis, over an angle equal to (minus) 90 degrees, which we wrote as:

transformation

The y-axis? What y-axis? What state filtering apparatus? Just relax. Think about what you’ve learned already. The orientations are shown below: the S apparatus separates ‘up’ and ‘down’ states along the z-axis, while the T-apparatus does so along an axis that is tilted, about the y-axis, over an angle equal to α, or φ, as it’s written in the table above.

tilted

Of course, we don’t really introduce an apparatus at this or that angle. We just introduced an electromagnetic field, which re-defined our | 1 〉 and | 2 〉 base states and, therefore, through the rotational transformation matrix, also defines our | I 〉 and | II 〉 base states.

[…] You may have lost me by now, and so then you’ll want to skip to the next section. That’s fine. Just remember that the representations in terms of | I 〉 and | II 〉 base states or in terms of | 1 〉 and | 2 〉 base states are mathematically equivalent. Having said that, if you’re reading this post, and you want to understand it, truly (because you want to truly understand quantum mechanics), then you should try to stick with me here. 🙂 Indeed, there’s a zillion things you could think about right now, but you should stick to the math now. Using that transformation matrix, we can relate the Cand CII coefficients in the | φ 〉 = | I 〉 CI + | II 〉 CII expression to the Cand CII coefficients in the | φ 〉 = | 1 〉 C1 + | 2 〉 C2 expression. Indeed, we wrote:

  • C= 〈 I | ψ 〉 = (1/√2)·(C1 − C2)
  • CII = 〈 II | ψ 〉 = (1/√2)·(C1 + C2)

That’s exactly the same as writing:

transformation

OK. […] Waw! You just took a huge leap, because we can now compare the two sets of differential equations:

set of equations

They’re mathematically equivalent, but the mathematical behavior of the functions involved is very different. Indeed, unlike the C1(t) and C2(t) amplitudes, we find that the CI(t) and CII(t) amplitudes are stationary, i.e. the associated probabilities – which we find by taking the absolute square of the amplitudes, as usual – do not vary in time. To be precise, if you write it all out and simplify, you’ll find that the CI(t) and CII(t) amplitudes are equal to:

  • CI(t) = 〈 I | ψ 〉 = (1/√2)·(C1 − C2) = (1/√2)·e(i/ħ)·(E0+ A)·t = (1/√2)·e(i/ħ)·EI·t
  • CII(t) = 〈 II | ψ 〉 = (1/√2)·(C1 + C2) = (1/√2)·e(i/ħ)·(E0− A)·t = (1/√2)·e(i/ħ)·EII·t

As the absolute square of the exponential is equal to one, the associated probabilities, i.e. |CI(t)|2 and |CII(t)|2, are, quite simply, equal to |1/√2|2 = 1/2. Now, it is very tempting to say that this means that our ammonia molecule has an equal chance to be in state I or state II. In fact, while I may have said something like that in my previous posts, that’s not how one should interpret this. The chance of our molecule being exactly in state I or state II, or in state 1 or state 2 is varying with time, with the probability being ‘dumped’ from one state to the other all of the time.

I mean… The electric dipole moment can point in any direction, really. So saying that our molecule has a 50/50 chance of being in state 1 or state 2 makes no sense. Likewise, saying that our molecule has a 50/50 chance of being in state I or state II makes no sense either. Indeed, the state of our molecule is specified by the | φ 〉 = | I 〉 CI + | II 〉 CII = | 1 〉 C1 + | 2 〉 Cequations, and neither of these two expressions is a stationary state. They mix two frequencies, because they mix two energy levels.

Having said that, we’re talking quantum mechanics here and, therefore, an external inhomogeneous electric field will effectively split the ammonia molecules according to their state. The situation is really like what a Stern-Gerlach apparatus does to a beam of electrons: it will split the beam according to the electron’s spin, which is either ‘up’ or, else, ‘down’, as shown in the graph below:

diagram 2

The graph for our ammonia molecule, shown below, is very similar. The vertical axis measures the same: energy. And the horizontal axis measures με, which increases with the strength of the electric field ε. So we see a similar ‘splitting’ of the energy of the molecule in an external electric field.

graph new

How should we explain this? It is very tempting to think that the presence of an external force field causes the electrons, or the ammonia molecule, to ‘snap into’ one of the two possible states, which are referred to as state I and state II respectively in the illustration of the ammonia state selector below. But… Well… Here we’re entering the murky waters of actually interpreting quantum mechanics, for which (a) we have no time, and (b) we are not qualified. So you should just believe, or take for granted, what’s being shown here: an inhomogeneous electric field will split our ammonia beam according to their state, which we define as I and II respectively, and which are associated with the energy E0+ A and E0− A  respectively.

electric field

As mentioned above, you should note that these two states are stationary. The Hamiltonian equations which, as they always do, describe the dynamics of this system, imply that the amplitude to go from state I to state II, or vice versa, is zero. To make sure you ‘get’ that, I reproduce the associated Hamiltonian matrix once again:

H-matrix I and II

Of course, that will change when we start our analysis of what’s happening in the maser. Indeed, we will have some non-zero HI,II and HII,I amplitudes in the resonant cavity of our ammonia maser, in which we’ll have an oscillating electric field and, as a result, induced transitions from state I to II and vice versa. However, that’s for later. While I’ll quickly insert the full picture diagram below, you should, for the moment, just think about those two stationary states and those two zeroes. 🙂

maser diagram

Capito? If not… Well… Start reading this post again, I’d say. 🙂

Intermezzo: on approximations

At this point, I need to say a few things about all of the approximations involved, because it can be quite confusing indeed. So let’s take a closer look at those energy levels and the related Hamiltonian coefficients. In fact, in his LecturesFeynman shows us that we can always have a general solution for the Hamiltonian equations describing a two-state system whenever we have constant Hamiltonian coefficients. That general solution – which, mind you, is derived assuming Hamiltonian coefficients that do not depend on time – can always be written in terms of two stationary base states, i.e. states with a definite energy and, hence, a constant probability. The equations, and the two definite energy levels are:

Hamiltonian

solution3

That yields the following values for the energy levels for the stationary states:

solution x

Now, that’s very different from the E= E0+ A and EII = E0− A energy levels for those stationary states we had defined in the previous section: those stationary states had no square root, and no μ2ε2, in their energy. In fact, that sort of answers the question: if there’s no external field, then that μ2ε2 factor is zero, and the square root in the expression becomes ±√A= ±A. So then we’re back to our E= E0+ A and EII = E0− A formulas. The whole point, however, is that we will actually have an electric field in that cavity. Moreover, it’s going to be a field that varies in time, which we’ll write:

field

Now, part of the confusion in Feynman’s approach is that he constantly switches between representing the system in terms of the I and II base states and the 1 and 2 base states respectively. For a good understanding, we should compare with our original representation of the dynamics in free space, for which the Hamiltonian was the following one:

H-matrix

That matrix can easily be related to the new one we’re going to have to solve, which is equal to:

H-matrix 2

The interpretation is easy if we look at that illustration again:

ammonia

If the direction of the electric dipole moment is opposite to the direction ε, then the associated energy is equal to −μ·ε = −μ·ε = −|μ|·|ε|·cosθ = −μ·ε·cos(π) = +με. Conversely, for state 2, we find −μ·ε·cos(0) = −με for the energy that’s associated with the dipole moment. You can and should think about the physics involved here, because they make sense! Thinking of amplitudes, you should note that the +με and −με terms effectively change the H11 and H22 coefficients, so they change the amplitude to stay in state 1 or state 2 respectively. That, of course, will have an impact on the associated probabilities, and so that’s why we’re talking of induced transitions now.

Having said that, the Hamiltonian matrix above keeps the −A for H12 and H21, so the matrix captures spontaneous transitions too!

Still… You may wonder why Feynman doesn’t use those Eand EII formulas with the square root because that would give us some exact solution, wouldn’t it? The answer to that question is: maybe it would, but would you know how to solve those equations? We’ll have a varying field, remember? So our Hamiltonian H11 and H22 coefficients will no longer be constant, but time-dependent. As you’re going to see, it takes Feynman three pages to solve the whole thing using the +με and −με approximation. So just imagine how complicated it would be using that square root expression! [By the way, do have a look at those asymptotic curves in that illustration showing the splitting of energy levels above, so you see how that approximation looks like.]

So that’s the real answer: we need to simplify somehow, so as to get any solutions at all!

Of course, it’s all quite confusing because, after Feynman first notes that, for strong fields, the A2 in that square root is small as compared to μ2ε2, thereby justifying the use of the simplified E= E0+ με = H11 and EII = E0− με = H22 coefficients, he continues and bluntly uses the very same square root expression to explain how that state selector works, saying that the electric field in the state selector will be rather weak and, hence, that με will be much smaller than A, so one can use the following approximation for the square root in the expressions above:

square root sum of squaresThe energy expressions then reduce to:energy 2

And then we can calculate the force on the molecules as:

force

So the electric field in the state selector is weak, but the electric field in the cavity is supposed to be strong, and so… Well… That’s it, really. The bottom line is that we’ve a beam of ammonia molecules that are all in state I, and it’s what happens with that beam then, that is being described by our new set of differential equations:

new

Solving the equations

As all molecules in our ammonia beam are described in terms of the | I 〉 and | II 〉 base states – as evidenced by the fact that we say all molecules that enter the cavity are state I – we need to switch to that representation. We do that by using that transformation above, so we write:

  • C= 〈 I | ψ 〉 = (1/√2)·(C1 − C2)
  • CII = 〈 II | ψ 〉 = (1/√2)·(C1 + C2)

Keeping these ‘definitions’ of Cand CII in mind, you should then add the two differential equations, divide the result by the square root of 2, and you should get the following new equation:

Eq1

Please! Do it and verify the result! You want to learn something here, no? 🙂

Likewise, subtracting the two differential equations, we get:

Eq2

We can re-write this as:set new

Now, the problem is that the Hamiltonian constants here are not constant. To be precise, the electric field ε varies in time. We wrote:

field

So HI,II  and HII,I, which are equal to με, are not constant: we’ve got Hamiltonian coefficients that are a function of time themselves. […] So… Well… We just need to get on with it and try to finally solve this thing. Let me just copy Feynman as he grinds through this:

F1

This is only the first step in the process. Feynman just takes two trial functions, which are really similar to the very general Ca·e–(i/ħ)·H11·t function we presented when only one equation was involved, or – if you prefer a set of two equations – those CI(t) = a·e(i/ħ)·EI·t and CI(t) = b·e(i/ħ)·EII·equations above. The difference is that the coefficients in front, i.e. γI and γII are not some (complex) constant, but functions of time themselves. The next step in the derivation is as follows:

F2

One needs to do a bit of gymnastics here as well to follow what’s going on, but please do check and you’ll see it works. Feynman derives another set of differential equations here, and they specify these γI = γI(t) and γII = γII(t) functions. These equations are written in terms of the frequency of the field, i.e. ω, and the resonant frequency ω0, which we mentioned above when calculating that 23.79 GHz frequency from the 2A = h·f0 equation. So ω0 is the same molecular resonance frequency but expressed as an angular frequency, so ω0 = f0/2π = ħ/2A. He then proceeds to simplify, using assumptions one should check. He then continues:

F3

That gives us what we presented in the previous post:

F4

So… Well… What to say? I explained those probability functions in my previous post, indeed. We’ve got two probabilities here:

  • P= cos2[(με0/ħ)·t]
  • PII = sin2[(με0/ħ)·t]

So that’s just like the P=  cos2[(A/ħ)·t] and P= sin2[(A/ħ)·t] probabilities we found for spontaneous transitions. But so here we are talking induced transitions.

As you can see, the frequency and, hence, the period, depend on the strength, or magnitude, of the electric field, i.e. the εconstant in the ε = 2ε0cos(ω·t) expression. The natural unit for measuring time would be the period once again, which we can easily calculate as (με0/ħ)·T = π ⇔ T = π·ħ/με0.

Now, we had that T = (π·ħ)/(2A) expression above, which allowed us to calculate the period of the spontaneous transition frequency, which we found was like 40 picoseconds, i.e. 40×10−12 seconds. Now, the T = (π·ħ)/(2με0) is very similar, it allows us to calculate the expected, average, or mean time for an induced transition. In fact, if we write Tinduced = (π·ħ)/(2με0) and Tspontaneous = (π·ħ)/(2A), then we can take ratio to find:

Tinduced/Tspontaneous = [(π·ħ)/(2με0)]/[(π·ħ)/(2A)] = A/με0

This A/με0 ratio is greater than one, so Tinduced/Tspontaneous is greater than one, which, in turn, means that the presence of our electric field – which, let me remind you, dances to the beat of the resonant frequency – causes a slower transition than we would have had if the oscillating electric field were not present.

But – Hey! – that’s the wrong comparison! Remember all molecules enter in a stationary state, as they’ve been selected so as to ensure they’re in state I. So there is no such thing as a spontaneous transition frequency here! They’re all polarized, so to speak, and they would remain that way if there was no field in the cavity. So if there was no oscillating electric field, they would never transition. Nothing would happen! Well… In terms of our particular set of base states, of course! Why? Well… Look at the Hamiltonian coefficients HI,II = HII,I = με: these coefficients are zero if ε is zero. So… Well… That says it all.

So that‘s what it’s all about: induced emission and, as I explained in my previous post, because all molecules enter in state I, i.e. the upper energy state, literally, they all ‘dump’ a net amount of energy equal to 2A into the cavity at the occasion of their first transition. The molecules then keep dancing, of course, and so they absorb and emit the same amount as they go through the cavity, but… Well… We’ve got a net contribution here, which is not only enough to maintain the cavity oscillations, but actually also provides a small excess of power that can be drawn from the cavity as microwave radiation of the same frequency.

As Feynman notes, an exact description of what actually happens requires an understanding of the quantum mechanics of the field in the cavity, i.e. quantum field theory, which I haven’t studied yet. But… Well… That’s for later, I guess. 🙂

Post scriptum: The sheer length of this post shows we’re not doing something that’s easy here. Frankly, I feel the whole analysis is still quite obscure, in the sense that – despite looking at this thing again and again – it’s hard to sort of interpret what’s going on, in a physical sense that is. But perhaps one shouldn’t try that. I’ve quoted Feynman’s view on how easy or how difficult it is to ‘understand’ quantum mechanics a couple of times already, so let me do it once more:

“Because atomic behavior is so unlike ordinary experience, it is very difficult to get used to, and it appears peculiar and mysterious to everyone—both to the novice and to the experienced physicist. Even the experts do not understand it the way they would like to, and it is perfectly reasonable that they should not, because all of direct, human experience and human intuition applies to large objects.”

So… Well… I’ll grind through the remaining Lectures now – I am halfway through Volume III now – and then re-visit all of this. Despite Feynman’s warning, I want to understand it the way I like to, even if I don’t quite know what way that is right now. 🙂

Addendum: As for those cycles and periods, I noted a couple of times already that the Planck-Einstein equation E = h·f  can usefully be re-written as E/= h, as it gives a physical interpretation to the value of the Planck constant. In fact, I said h is the energy that’s associated with one cycle, regardless of the frequency of the radiation involved. Indeed, the energy of a photon divided by the number of cycles per second, should give us the energy per cycle, no?

Well… Yes and no. Planck’s constant h and the frequency are both expressed referencing the time unit. However, if we say that a sodium atom emits one photon only as its electron transitions from a higher energy level to a lower one, and if we say that involves a decay time of the order of 3.2×10−8 seconds, then what we’re saying really is that a sodium light photon will ‘pack’ like 16 million cycles, which is what we get when we multiply the number of cycles per second (i.e. the mentioned frequency of 500×1012 Hz) by the decay time (i.e. 3.2×10−8 seconds): (500×1012 Hz)·(3.2×10−8 s) = 16 ×10cycles, indeed. So the energy per cycle is 2.068 eV (i.e. the photon energy) divided by 16×106, so that’s 0.129×10−6 eV. Unsurprisingly, that’s what we get when we we divide h by 3.2×10−8 s: (4.13567×10−15)/(3.2×10−8 s) = 1.29×10−7 eV. We’re just putting some values in to the E/(T) = h/T equation here.

The logic for that 2A = h·f0 is the same. The frequency of the radiation that’s being absorbed or emitted is 23.79 GHz, so the photon energy is (23.97×109 Hz)·(4.13567×10−15 eV·s) ≈ 1×10−4 eV. Now, we calculated the transition period T as T = π·ħ/A ≈ (π·6.626×10−16 eV·s)/(0.5×10−4 eV) ≈ 41.6×10−12 seconds. Now, an oscillation of a frequency of 23.97 giga-hertz that only lasts 41.6×10−12 seconds is an oscillation of one cycle only. The consequence is that, when we continue this style of reasoning, we’d have a photon that packs all of its energy into one cycle!

Let’s think about what this implies in terms of the density in space. The wavelength of our microwave radiation is 1.25×10−2 m, so we’ve got a ‘density’ of 1×10−4 eV/1.25×10−2 m = 0.8×10−2 eV/m = 0.008 eV/m. The wavelength of our sodium light is 0.6×10−6 m, so we get a ‘density’ of 1.29×10−7 eV/0.6×10−6 m = 2.15×10−1 eV/m = 0.215 eV/m. So the energy ‘density’ of our sodium light is 26.875 times that of our microwave radiation. 🙂

Frankly, I am not quite sure if calculations like this make much sense. In fact, when talking about energy densities, I should review my posts on the Poynting vector. However, they may help you think things through. 🙂

Occam’s Razor

The analysis of a two-state system (i.e. the rather famous example of an ammonia molecule ‘flipping’ its spin direction from ‘up’ to ‘down’, or vice versa) in my previous post is a good opportunity to think about Occam’s Razor once more. What are we doing? What does the math tell us?

In the example we chose, we didn’t need to worry about space. It was all about time: an evolving state over time. We also knew the answers we wanted to get: if there is some probability for the system to ‘flip’ from one state to another, we know it will, at some point in time. We also want probabilities to add up to one, so we knew the graph below had to be the result we would find: if our molecule can be in two states only, and it starts of in one, then the probability that it will remain in that state will gradually decline, while the probability that it flips into the other state will gradually increase, which is what is depicted below.

graph

However, the graph above is only a Platonic idea: we don’t bother to actually verify what state the molecule is in. If we did, we’d have to ‘re-set’ our t = 0 point, and start all over again. The wavefunction would collapse, as they say, because we’ve made a measurement. However, having said that, yes, in the physicist’s Platonic world of ideas, the probability functions above make perfect sense. They are beautiful. You should note, for example, that P1 (i.e. the probability to be in state 1) and P2 (i.e. the probability to be in state 2) add up to 1 all of the time, so we don’t need to integrate over a cycle or something: so it’s all perfect!

These probability functions are based on ideas that are even more Platonic: interfering amplitudes. Let me explain.

Quantum physics is based on the idea that these probabilities are determined by some wavefunction, a complex-valued amplitude that varies in time and space. It’s a two-dimensional thing, and then it’s not. It’s two-dimensional because it combines a sine and cosine, i.e. a real and an imaginary part, but the argument of the sine and the cosine is the same, and the sine and cosine are the same function, except for a phase shift equal to π. We write:

a·eiθ = cos(θ) – sin(−θ) = cosθ – sinθ

The minus sign is there because it turns out that Nature measures angles, i.e. our phase, clockwise, rather than counterclockwise, so that’s not as per our mathematical convention. But that’s a minor detail, really. [It should give you some food for thought, though.] For the rest, the related graph is as simple as the formula:

graph sin and cos

Now, the phase of this wavefunction is written as θ = (ω·t − k ∙x). Hence, ω determines how this wavefunction varies in time, and the wavevector k tells us how this wave varies in space. The young Frenchman Comte Louis de Broglie noted the mathematical similarity between the ω·t − k ∙x expression and Einstein’s four-vector product pμxμ = E·t − px, which remains invariant under a Lorentz transformation. He also understood that the Planck-Einstein relation E = ħ·ω actually defines the energy unit and, therefore, that any frequency, any oscillation really, in space or in time, is to be expressed in terms of ħ.

[To be precise, the fundamental quantum of energy is h = ħ·2π, because that’s the energy of one cycle. To illustrate the point, think of the Planck-Einstein relation. It gives us the energy of a photon with frequency f: Eγ = h·f. If we re-write this equation as Eγ/f = h, and we do a dimensional analysis, we get: h = Eγ/f ⇔ 6.626×10−34 joule·second [x joule]/[cycles per second] ⇔ h = 6.626×10−34 joule per cycle. It’s only because we are expressing ω and k as angular frequencies (i.e. in radians per second or per meter, rather than in cycles per second or per meter) that we have to think of ħ = h/2π rather than h.]

Louis de Broglie connected the dots between some other equations too. He was fully familiar with the equations determining the phase and group velocity of composite waves, or a wavetrain that actually might represent a wavicle traveling through spacetime. In short, he boldly equated ω with ω = E/ħ and k with k = p/ħ, and all came out alright. It made perfect sense!

I’ve written enough about this. What I want to write about here is how this also makes for the situation on hand: a simple two-state system that depends on time only. So its phase is θ = ω·t = E0/ħ. What’s E0? It is the total energy of the system, including the equivalent energy of the particle’s rest mass and any potential energy that may be there because of the presence of one or the other force field. What about kinetic energy? Well… We said it: in this case, there is no translational or linear momentum, so p = 0. So our Platonic wavefunction reduces to:

a·eiθ = ae(i/ħ)·(E0·t)

Great! […] But… Well… No! The problem with this wavefunction is that it yields a constant probability. To be precise, when we take the absolute square of this wavefunction – which is what we do when calculating a probability from a wavefunction − we get P = a2, always. The ‘normalization’ condition (so that’s the condition that probabilities have to add up to one) implies that P1 = P2 = a2 = 1/2. Makes sense, you’ll say, but the problem is that this doesn’t reflect reality: these probabilities do not evolve over time and, hence, our ammonia molecule never ‘flips’ its spin direction from ‘up’ to ‘down’, or vice versa. In short, our wavefunction does not explain reality.

The problem is not unlike the problem we’d had with a similar function relating the momentum and the position of a particle. You’ll remember it: we wrote it as a·eiθ = ae(i/ħ)·(p·x). [Note that we can write a·eiθ = a·e−(i/ħ)·(E0·t − p·x) = a·e−(i/ħ)·(E0·t)·e(i/ħ)·(p·x), so we can always split our wavefunction in a ‘time’ and a ‘space’ part.] But then we found that this wavefunction also yielded a constant and equal probability all over space, which implies our particle is everywhere (and, therefore, nowhere, really).

In quantum physics, this problem is solved by introducing uncertainty. Introducing some uncertainty about the energy, or about the momentum, is mathematically equivalent to saying that we’re actually looking at a composite wave, i.e. the sum of a finite or infinite set of component waves. So we have the same ω = E/ħ and k = p/ħ relations, but we apply them to n energy levels, or to some continuous range of energy levels ΔE. It amounts to saying that our wave function doesn’t have a specific frequency: it now has n frequencies, or a range of frequencies Δω = ΔE/ħ.

We know what that does: it ensures our wavefunction is being ‘contained’ in some ‘envelope’. It becomes a wavetrain, or a kind of beat note, as illustrated below:

File-Wave_group

[The animation also shows the difference between the group and phase velocity: the green dot shows the group velocity, while the red dot travels at the phase velocity.]

This begs the following question: what’s the uncertainty really? Is it an uncertainty in the energy, or is it an uncertainty in the wavefunction? I mean: we have a function relating the energy to a frequency. Introducing some uncertainty about the energy is mathematically equivalent to introducing uncertainty about the frequency. Of course, the answer is: the uncertainty is in both, so it’s in the frequency and in the energy and both are related through the wavefunction. So… Well… Yes. In some way, we’re chasing our own tail. 🙂

However, the trick does the job, and perfectly so. Let me summarize what we did in the previous post: we had the ammonia molecule, i.e. an NH3 molecule, with the nitrogen ‘flipping’ across the hydrogens from time to time, as illustrated below:

dipole

This ‘flip’ requires energy, which is why we associate two energy levels with the molecule, rather than just one. We wrote these two energy levels as E+ A and E− A. That assumption solved all of our problems. [Note that we don’t specify what the energy barrier really consists of: moving the center of mass obviously requires some energy, but it is likely that a ‘flip’ also involves overcoming some electrostatic forces, as shown by the reversal of the electric dipole moment in the illustration above.] To be specific, it gave us the following wavefunctions for the amplitude to be in the ‘up’ or ‘1’ state versus the ‘down’ or ‘2’ state respectivelly:

  • C= (1/2)·e(i/ħ)·(E− A)·t + (1/2)·e(i/ħ)·(E+ A)·t
  • C= (1/2)·e(i/ħ)·(E− A)·t – (1/2)·e(i/ħ)·(E+ A)·t

Both are composite waves. To be precise, they are the sum of two component waves with a temporal frequency equal to ω= (E− A)/ħ and ω= (E+ A)/ħ respectively. [As for the minus sign in front of the second term in the wave equation for C2, −1 = e±iπ, so + (1/2)·e(i/ħ)·(E+ A)·t and – (1/2)·e(i/ħ)·(E+ A)·t are the same wavefunction: they only differ because their relative phase is shifted by ±π.] So the so-called base states of the molecule themselves are associated with two different energy levels: it’s not like one state has more energy than the other.

You’ll say: so what?

Well… Nothing. That’s it really. That’s all I wanted to say here. The absolute square of those two wavefunctions gives us those time-dependent probabilities above, i.e. the graph we started this post with. So… Well… Done!

You’ll say: where’s the ‘envelope’? Oh! Yes! Let me tell you. The C1(t) and C2(t) equations can be re-written as:

C2

Now, remembering our rules for adding and subtracting complex conjugates (eiθ + e–iθ = 2cosθ and eiθ − e–iθ = 2sinθ), we can re-write this as:

C3

So there we are! We’ve got wave equations whose temporal variation is basically defined by Ebut, on top of that, we have an envelope here: the cos(A·t/ħ) and sin(A·t/ħ) factor respectively. So their magnitude is no longer time-independent: both the phase as well as the amplitude now vary with time. The associated probabilities are the ones we plotted:

  • |C1(t)|= cos2[(A/ħ)·t], and
  • |C2(t)|= sin2[(A/ħ)·t].

So, to summarize it all once more, allowing the nitrogen atom to push its way through the three hydrogens, so as to flip to the other side, thereby breaking the energy barrier, is equivalent to associating two energy levels to the ammonia molecule as a whole, thereby introducing some uncertainty, or indefiniteness as to its energy, and that, in turn, gives us the amplitudes and probabilities that we’ve just calculated. [And you may want to note here that the probabilities “sloshing back and forth”, or “dumping into each other” – as Feynman puts it – is the result of the varying magnitudes of our amplitudes, so that’s the ‘envelope’ effect. It’s only because the magnitudes vary in time that their absolute square, i.e. the associated probability, varies too.

So… Well… That’s it. I think this and all of the previous posts served as a nice introduction to quantum physics. More in particular, I hope this post made you appreciate the mathematical framework is not as horrendous as it often seems to be.

When thinking about it, it’s actually all quite straightforward, and it surely respects Occam’s principle of parsimony in philosophical and scientific thought, also know as Occam’s Razor: “When trying to explain something, it is vain to do with more what can be done with less.” So the math we need is the math we need, really: nothing more, nothing less. As I’ve said a couple of times already, Occam would have loved the math behind QM: the physics call for the math, and the math becomes the physics.

That’s what makes it beautiful. 🙂

Post scriptum:

One might think that the addition of a term in the argument in itself would lead to a beat note and, hence, a varying probability but, no! We may look at e(i/ħ)·(E+ A)·t as a product of two amplitudes:

e(i/ħ)·(E+ A)·t e(i/ħ)·E0·t·e(i/ħ)·A·t

But, when writing this all out, one just gets a cos(α·t+β·t)–sin(α·t+β·t), whose absolute square |cos(α·t+β·t)–sin(α·t+β·t)|= 1. However, writing e(i/ħ)·(E+ A)·t as a product of two amplitudes in itself is interesting. We multiply amplitudes when an event consists of two sub-events. For example, the amplitude for some particle to go from s to x via some point a is written as:

x | s 〉via a = 〈 x | a 〉〈 a | s 〉

Having said that, the graph of the product is uninteresting: the real and imaginary part of the wavefunction are a simple sine and cosine function, and their absolute square is constant, as shown below. graph

Adding two waves with very different frequencies – A is a fraction of E– gives a much more interesting pattern, like the one below, which shows an eiαt+eiβt = cos(αt)−i·sin(αt)+cos(βt)−i·sin(βt) = cos(αt)+cos(βt)−i·[sin(αt)+sin(βt)] pattern for α = 1 and β = 0.1.

graph 2

That doesn’t look a beat note, does it? The graphs below, which use 0.5 and 0.01 for β respectively, are not typical beat notes either.

 graph 3graph 4

We get our typical ‘beat note’ only when we’re looking at a wave traveling in space, so then we involve the space variable again, and the relations that come with in, i.e. a phase velocity v= ω/k  = (E/ħ)/(p/ħ) = E/p = c2/v (read: all component waves travel at the same speed), and a group velocity v= dω/dk = v (read: the composite wave or wavetrain travels at the classical speed of our particle, so it travels with the particle, so to speak). That’s what’s I’ve shown numerous times already, but I’ll insert one more animation here, just to make sure you see what we’re talking about. [Credit for the animation goes to another site, one on acoustics, actually!]

beats

So what’s left? Nothing much. The only thing you may want to do is to continue thinking about that wavefunction. It’s tempting to think it actually is the particle, somehow. But it isn’t. So what is it then? Well… Nobody knows, really, but I like to think it does travel with the particle. So it’s like a fundamental property of the particle. We need it every time when we try to measure something: its position, its momentum, its spin (i.e. angular momentum) or, in the example of our ammonia molecule, its orientation in space. So the funny thing is that, in quantum mechanics,

  1. We can measure probabilities only, so there’s always some randomness. That’s how Nature works: we don’t really know what’s happening. We don’t know the internal wheels and gears, so to speak, or the ‘hidden variables’, as one interpretation of quantum mechanics would say. In fact, the most commonly accepted interpretation of quantum mechanics says there are no ‘hidden variables’.
  2. But then, as Polonius famously put, there is a method in this madness, and the pioneers – I mean Werner Heisenberg, Louis de Broglie, Niels Bohr, Paul Dirac, etcetera – discovered. All probabilities can be found by taking the square of the absolute value of a complex-valued wavefunction (often denoted by Ψ), whose argument, or phase (θ), is given by the de Broglie relations ω = E/ħ and k = p/ħ:

θ = (ω·t − k ∙x) = (E/ħ)·t − (p/ħ)·x

That should be obvious by now, as I’ve written dozens of posts on this by now. 🙂 I still have trouble interpreting this, however—and I am not ashamed, because the Great Ones I just mentioned have trouble with that too. But let’s try to go as far as we can by making a few remarks:

  •  Adding two terms in math implies the two terms should have the same dimension: we can only add apples to apples, and oranges to oranges. We shouldn’t mix them. Now, the (E/ħ)·t and (p/ħ)·x terms are actually dimensionless: they are pure numbers. So that’s even better. Just check it: energy is expressed in newton·meter (force over distance, remember?) or electronvolts (1 eV = 1.6×10−19 J = 1.6×10−19 N·m); Planck’s constant, as the quantum of action, is expressed in J·s or eV·s; and the unit of (linear) momentum is 1 N·s = 1 kg·m/s = 1 N·s. E/ħ gives a number expressed per second, and p/ħ a number expressed per meter. Therefore, multiplying it by t and x respectively gives us a dimensionless number indeed.
  • It’s also an invariant number, which means we’ll always get the same value for it. As mentioned above, that’s because the four-vector product pμxμ = E·t − px is invariant: it doesn’t change when analyzing a phenomenon in one reference frame (e.g. our inertial reference frame) or another (i.e. in a moving frame).
  • Now, Planck’s quantum of action h or ħ (they only differ in their dimension: h is measured in cycles per second and ħ is measured in radians per second) is the quantum of energy really. Indeed, if “energy is the currency of the Universe”, and it’s real and/or virtual photons who are exchanging it, then it’s good to know the currency unit is h, i.e. the energy that’s associated with one cycle of a photon.
  • It’s not only time and space that are related, as evidenced by the fact that t − x itself is an invariant four-vector, E and p are related too, of course! They are related through the classical velocity of the particle that we’re looking at: E/p = c2/v and, therefore, we can write: E·β = p·c, with β = v/c, i.e. the relative velocity of our particle, as measured as a ratio of the speed of light. Now, I should add that the t − x four-vector is invariant only if we measure time and space in equivalent units. Otherwise, we have to write c·t − x. If we do that, so our unit of distance becomes meter, rather than one meter, or our unit of time becomes the time that is needed for light to travel one meter, then = 1, and the E·β = p·c becomes E·β = p, which we also write as β = p/E: the ratio of the energy and the momentum of our particle is its (relative) velocity.

Combining all of the above, we may want to assume that we are measuring energy and momentum in terms of the Planck constant, i.e. the ‘natural’ unit for both. In addition, we may also want to assume that we’re measuring time and distance in equivalent units. Then the equation for the phase of our wavefunctions reduces to:

θ = (ω·t − k ∙x) = E·t − p·x

Now, θ is the argument of a wavefunction, and we can always re-scale such argument by multiplying or dividing it by some constant. It’s just like writing the argument of a wavefunction as v·t–x or (v·t–x)/v = t –x/v  with the velocity of the waveform that we happen to be looking at. [In case you have trouble following this argument, please check the post I did for my kids on waves and wavefunctions.] Now, the energy conservation principle tells us the energy of a free particle won’t change. [Just to remind you, a ‘free particle’ means it is present in a ‘field-free’ space, so our particle is in a region of uniform potential.] You see what I am going to do now: we can, in this case, treat E as a constant, and divide E·t − p·x by E, so we get a re-scaled phase for our wavefunction, which I’ll write as:

φ = (E·t − p·x)/E = t − (p/E)·x = t − β·x

Now that’s the argument of a wavefunction with the argument expressed in distance units. Alternatively, we could also look at p as some constant, as there is no variation in potential energy that will cause a change in momentum, i.e. in kinetic energy. We’d then divide by p and we’d get (E·t − p·x)/p = (E/p)·t − x) = t/β − x, which amounts to the same, as we can always re-scale by multiplying it with β, which would then yield the same t − β·x argument.

The point is, if we measure energy and momentum in terms of the Planck unit (I mean: in terms of the Planck constant, i.e. the quantum of energy), and if we measure time and distance in ‘natural’ units too, i.e. we take the speed of light to be unity, then our Platonic wavefunction becomes as simple as:

Φ(φ) = a·eiφ = a·ei(t − β·x)

This is a wonderful formula, but let me first answer your most likely question: why would we use a relative velocity?Well… Just think of it: when everything is said and done, the whole theory of relativity and, hence, the whole of physics, is based on one fundamental and experimentally verified fact: the speed of light is absolute. In whatever reference frame, we will always measure it as 299,792,458 m/s. That’s obvious, you’ll say, but it’s actually the weirdest thing ever if you start thinking about it, and it explains why those Lorentz transformations look so damn complicated. In any case, this fact legitimately establishes as some kind of absolute measure against which all speeds can be measured. Therefore, it is only natural indeed to express a velocity as some number between 0 and 1. Now that amounts to expressing it as the β = v/c ratio.

Let’s now go back to that Φ(φ) = a·eiφ = a·ei(t − β·x) wavefunction. Its temporal frequency ω is equal to one, and its spatial frequency k is equal to β = v/c. It couldn’t be simpler but, of course, we’ve got this remarkably simple result because we re-scaled the argument of our wavefunction using the energy and momentum itself as the scale factor. So, yes, we can re-write the wavefunction of our particle in a particular elegant and simple form using the only information that we have when looking at quantum-mechanical stuff: energy and momentum, because that’s what everything reduces to at that level.

Of course, the analysis above does not include uncertainty. Our information on the energy and the momentum of our particle will be incomplete: we’ll write E = E± σE, and p = p± σp. [I am a bit tired of using the Δ symbol, so I am using the σ symbol here, which denotes a standard deviation of some density function. It underlines the probabilistic, or statistical, nature of our approach.] But, including that, we’ve pretty much explained what quantum physics is about here.

You just need to get used to that complex exponential: eiφ = cos(−φ) + i·sin(−φ) = cos(φ) − i·sin(φ). Of course, it would have been nice if Nature would have given us a simple sine or cosine function. [Remember the sine and cosine function are actually the same, except for a phase difference of 90 degrees: sin(φ) = cos(π/2−φ) = cos(φ+π/2). So we can go always from one to the other by shifting the origin of our axis.] But… Well… As we’ve shown so many times already, a real-valued wavefunction doesn’t explain the interference we observe, be it interference of electrons or whatever other particles or, for that matter, the interference of electromagnetic waves itself, which, as you know, we also need to look at as a stream of photons , i.e. light quanta, rather than as some kind of infinitely flexible aether that’s undulating, like water or air.

So… Well… Just accept that eiφ is a very simple periodic function, consisting of two sine waves rather than just one, as illustrated below.

 sine

And then you need to think of stuff like this (the animation is taken from Wikipedia), but then with a projection of the sine of those phasors too. It’s all great fun, so I’ll let you play with it now. 🙂

Sumafasores

The Hamiltonian for a two-state system: the ammonia example

Ammonia, i.e. NH3, is a colorless gas with a strong smell. Its serves as a precursor in the production of fertilizer, but we also know it as a cleaning product, ammonium hydroxide, which is NH3 dissolved in water. It has a lot of other uses too. For example, its use in this post, is to illustrate a two-state system. 🙂 We’ll apply everything we learned in our previous posts and, as I  mentioned when finishing the last of those rather mathematical pieces, I think the example really feels like a reward after all of the tough work on all of those abstract concepts – like that Hamiltonian matrix indeed – so I hope you enjoy it. So… Here we go!

The geometry of the NH3 molecule can be described by thinking of it as a trigonal pyramid, with the nitrogen atom (N) at its apex, and the three hydrogen atoms (H) at the base, as illustrated below. [Feynman’s illustration is slightly misleading, though, because it may give the impression that the hydrogen atoms are bonded together somehow. That’s not the case: the hydrogen atoms share their electron with the nitrogen, thereby completing the outer shell of both atoms. This is referred to as a covalent bond. You may want to look it up, but it is of no particular relevance to what follows here.]

Capture

Here, we will only worry about the spin of the molecule about its axis of symmetry, as shown above, which is either in one direction or in the other, obviously. So we’ll discuss the molecule as a two-state system. So we don’t care about its translational (i.e. linear) momentum, its internal vibrations, or whatever else that might be going on. It is one of those situations illustrating that the spin vector, i.e. the vector representing angular momentum, is an axial vector: the first state, which is denoted by | 1 〉 is not the mirror image of state | 2 〉. In fact, there is a more sophisticated version of the illustration above, which usefully reminds us of the physics involved.

dipoleIt should be noted, however, that we don’t need to specify what the energy barrier really consists of: moving the center of mass obviously requires some energy, but it is likely that a ‘flip’ also involves overcoming some electrostatic forces, as shown by the reversal of the electric dipole moment in the illustration above. In fact, the illustration may confuse you, because we’re usually thinking about some net electric charge that’s spinning, and so the angular momentum results in a magnetic dipole moment, that’s either ‘up’ or ‘down’, and it’s usually also denoted by the very same μ symbol that’s used below. As I explained in my post on angular momentum and the magnetic moment, it’s related to the angular momentum J through the so-called g-number. In the illustration above, however, the μ symbol is used to denote an electric dipole moment, so that’s different. Don’t rack your brain over it: just accept there’s an energy barrier, and it requires energy to get through it. Don’t worry about its details!

Indeed, in quantum mechanics, we abstract away from such nitty-gritty, and so we just say that we have base states | i 〉 here, with i equal to 1 or 2. One or the other. Now, in our post on quantum math, we introduced what Feynman only half-jokingly refers to as the Great Law of Quantum Physics: | = ∑ | i 〉〈 i | over all base states i. It basically means that we should always describe our initial and end states in terms of base states. Applying that principle to the state of our ammonia molecule, which we’ll denote by | ψ 〉, we can write:

f1

You may – in fact, you should – mechanically apply that | = ∑ | i 〉〈 i | substitution to | ψ 〉 to get what you get here, but you should also think about what you’re writing. It’s not an easy thing to interpret, but it may help you to think of the similarity of the formula above with the description of a vector in terms of its base vectors, which we write as A = Ax·e+ Ay·e2 + Az·e3. Just substitute the Acoefficients for Ci and the ebase vectors for the | i 〉 base states, and you may understand this formula somewhat better. It also explains why the | ψ 〉 state is often referred to as the | ψ 〉 state vector: unlike our  A = ∑ Ai·esum of base vectors, our | 1 〉 C1 + | 2 〉 Csum does not have any geometrical interpretation but… Well… Not all ‘vectors’ in math have a geometric interpretation, and so this is a case in point.

It may also help you to think of the time-dependency. Indeed, this formula makes a lot more sense when realizing that the state of our ammonia molecule, and those coefficients Ci, depend on time, so we write: ψ = ψ(t) and C= Ci(t). Hence, if we would know, for sure, that our molecule is always in state | 1 〉, then C1 = 1 and C2 = 0, and we’d write: | ψ 〉 = | 1 〉 = | 1 〉 1 + | 2 〉 0. [I am always tempted to insert a little dot (·), and change the order of the factors, so as to show we’re talking some kind of product indeed – so I am tempted to write | ψ 〉 = C1·| 1 〉 C1 + C2·| 2 〉 C2, but I note that’s not done conventionally, so I won’t do it either.]  

Why this time dependency? It’s because we’ll allow for the possibility of the nitrogen to push its way through the pyramid – through the three hydrogens, really – and flip to the other side. It’s unlikely, because it requires a lot of energy to get half-way through (we’ve got what we referred to as an energy barrier here), but it may happen and, as we’ll see shortly, it results in us having to think of the the ammonia molecule as having two separate energy levels, rather than just one. We’ll denote those energy levels as E0 ± A. However, I am getting ahead of myself here, so let me get back to the main story.

To fully understand the story, you should really read my previous post on the Hamiltonian, which explains how those Ci coefficients, as a function of time, can be determined. They’re determined by a set of differential equations (i.e. equations involving a function and the derivative of that function) which we wrote as:

H6

 If we have two base states only – which is the case here – then this set of equations is:

set - two-base

Two equations and two functions – C= C1(t) and C= C2(t) – so we should be able to solve this thing, right? Well… No. We don’t know those Hij coefficients. As I explained in my previous post, they also evolve in time, so we should write them as Hij(t) instead of Hij tout court, and so it messes the whole thing up. We have two equations and six functions really. There is no way we can solve this! So how do we get out of this mess?

Well… By trial and error, I guess. 🙂 Let us just assume the molecule would behave nicely—which we know it doesn’t, but so let’s push the ‘classical’ analysis as far as we can, so we might get some clues as to how to solve this problem. In fact, our analysis isn’t ‘classical’ at all, because we’re still talking amplitudes here! However, you’ll agree the ‘simple’ solution would be that our ammonia molecule doesn’t ‘tunnel’. It just stays in the same spin direction forever. Then H12 and H21 must be zero (think of the U12(t + Δt, t) and U21(t + Δt, t) functions) and H11 and H22 are equal to… Well… I’d love to say they’re equal to 1 but… Well… You should go through my previous posts: these Hamiltonian coefficients are related to probabilities but… Well… Same-same but different, as they say in Asia. 🙂 They’re amplitudes, which are things you use to calculate probabilities. But calculating probabilities involve normalization and other stuff, like allowing for interference of amplitudes, and so… Well… To make a long story short, if our ammonia molecule would stay in the same spin direction forever, then H11 and H22  are not one but some constant. In any case, the point is that they would not change in time (so H11(t) = H11  and H22(t ) = H22), and, therefore, our two equations would reduce to:

S1

So the coefficients are now proper coefficients, in the sense that they’ve got some definite value, and so we have two equations and two functions only now, and so we can solve this. Indeed, remembering all of the stuff we wrote on the magic of exponential functions (more in particular, remembering that d[ex]/dx), we can understand the proposed solution:

S2

As Feynman notes: “These are just the amplitudes for stationary states with the energies E= H11 and E= H22.” Now let’s think about that. Indeed, I find the term ‘stationary’ state quite confusing, as it’s ill-defined. In this context, it basically means that we have a wavefunction that is determined by (i) a definite (i.e. unambiguous, or precise) energy level and (ii) that there is no spatial variation. Let me refer you to my post on the basics of quantum math here. We often use a sort of ‘Platonic’ example of the wavefunction indeed:

a·ei·θ ei·(ω·t − k ∙x) = a·e(i/ħ)·(E·t − px)

So that’s a wavefunction assuming the particle we’re looking at has some well-defined energy E and some equally well-defined momentum p. Now, that’s kind of ‘Platonic’ indeed, because it’s more like an idea, rather than something real. Indeed, a wavefunction like that means that the particle is everywhere and nowhere, really—because its wavefunction is spread out all of over space. Of course, we may think of the ‘space’ as some kind of confined space, like a box, and then we can think of this particle as being ‘somewhere’ in that box, and then we look at the temporal variation of this function only – which is what we’re doing now: we don’t consider the space variable x at all. So then the equation reduces to a·e–(i/ħ)·(E·t), and so… Well… Yes. We do find that our Hamiltonian coefficient Hii is like the energy of the | i 〉 state of our NH3 molecule, so we write: H11 = E1, and H22 = E2, and the ‘wavefunctions’ of our Cand Ccoefficients can be written as:

  • Ca·e(i/ħ)·(H11·t) a·e(i/ħ)·(E1·t), with H11 = E1, and
  • C= a·e(i/ħ)·(H22·t) a·e(i/ħ)·(E2·t), with H22 = E2.

But can we interpret Cand  Cas proper amplitudes? They are just coefficients in these equations, aren’t they? Well… Yes and no. From what we wrote in previous posts, you should remember that these Ccoefficients are equal to 〈 i | ψ 〉, so they are the amplitude to find our ammonia molecule in one state or the other.

Back to Feynman now. He adds, logically but brilliantly:

We note, however, that for the ammonia molecule the two states |1〉 and |2〉 have a definite symmetry. If nature is at all reasonable, the matrix elements H11 and H22 must be equal. We’ll call them both E0, because they correspond to the energy the states would have if H11 and H22 were zero.”

So our Cand Camplitudes then reduce to:

  • C〈 1 | ψ 〉 = a·e(i/ħ)·(E0·t)
  • C=〈 2 | ψ 〉 = a·e(i/ħ)·(E0·t)

We can now take the absolute square of both to find the probability for the molecule to be in state 1 or in state 2:

  • |〈 1 | ψ 〉|= |a·e(i/ħ)·(E0·t)|a
  • |〈 2 | ψ 〉|= |a·e(i/ħ)·(E0·t)|a

Now, the probabilities have to add up to 1, so a+ a= 1 and, therefore, the probability to be in either in state 1 or state 2 is 0.5, which is what we’d expect.

Note: At this point, it is probably good to get back to our | ψ 〉 = | 1 〉 C1 + | 2 〉 Cequation, so as to try to understand what it really says. Substituting the a·e(i/ħ)·(E0·t) expression for C1 and C2 yields:

| ψ 〉 = | 1 〉 a·e(i/ħ)·(E0·t) + | 2 〉 a·e(i/ħ)·(E0·t) = [| 1 〉 + | 2 〉] a·e(i/ħ)·(E0·t)

Now, what is this saying, really? In our previous post, we explained this is an ‘open’ equation, so it actually doesn’t mean all that much: we need to ‘close’ or ‘complete’ it by adding a ‘bra’, i.e. a state like 〈 χ |, so we get a 〈 χ | ψ〉 type of amplitude that we can actually do something with. Now, in this case, our final 〈 χ | state is either 〈 1 | or 〈 2 |, so we write:

  • 〈 1 | ψ 〉 = [〈 1 | 1 〉 + 〈 1 | 2 〉]·a·e(i/ħ)·(E0·t) = [1 + 0]·a·e(i/ħ)·(E0·t)· = a·e(i/ħ)·(E0·t)
  • 〈 2 | ψ 〉 = [〈 2 | 1 〉 + 〈 2 | 2 〉]·a·e(i/ħ)·(E0·t) = [0 + 1]·a·e(i/ħ)·(E0·t)· = a·e(i/ħ)·(E0·t)

Note that I finally added the multiplication dot (·) because we’re talking proper amplitudes now and, therefore, we’ve got a proper product too: we multiply one complex number with another. We can now take the absolute square of both to find the probability for the molecule to be in state 1 or in state 2:

  • |〈 1 | ψ 〉|= |a·e(i/ħ)·(E0·t)|a
  • |〈 2 | ψ 〉|= |a·e(i/ħ)·(E0·t)|a

Unsurprisingly, we find the same thing: these probabilities have to add up to 1, so a+ a= 1 and, therefore, the probability to be in state 1 or state 2 is 0.5. So the notation and the logic behind makes perfect sense. But let me get back to the lesson now.

The point is: the true meaning of a ‘stationary’ state here, is that we have non-fluctuating probabilities. So they are and remain equal to some constant, i.e. 1/2 in this case. This implies that the state of the molecule does not change: there is no way to go from state 1 to state 2 and vice versa. Indeed, if we know the molecule is in state 1, it will stay in that state. [Think about what normalization of probabilities means when we’re looking at one state only.]

You should note that these non-varying probabilities are related to the fact that the amplitudes have a non-varying magnitude. The phase of these amplitudes varies in time, of course, but their magnitude is and remains aalways. The amplitude is not being ‘enveloped’ by another curve, so to speak.

OK. That should be clear enough. Sorry I spent so much time on this, but this stuff on ‘stationary’ states comes back again and again and so I just wanted to clear that up as much as I can. Let’s get back to the story.

So we know that, what we’re describing above, is not what ammonia does really. As Feynman puts it: “The equations [i.e. the Cand Cequations above] don’t tell us what what ammonia really does. It turns out that it is possible for the nitrogen to push its way through the three hydrogens and flip to the other side. It is quite difficult; to get half-way through requires a lot of energy. How can it get through if it hasn’t got enough energy? There is some amplitude that it will penetrate the energy barrier. It is possible in quantum mechanics to sneak quickly across a region which is illegal energetically. There is, therefore, some [small] amplitude that a molecule which starts in |1〉 will get to the state |2. The coefficients H12 and H21 are not really zero.”

He adds: “Again, by symmetry, they should both be the same—at least in magnitude. In fact, we already know that, in general, Hij must be equal to the complex conjugate of Hji.”

His next step, then, is to interpreted as either a stroke of genius or, else, as unexplained. 🙂 He invokes the symmetry of the situation to boldly state that H12 is some real negative number, which he denotes as −A, which – because it’s a real number (so the imaginary part is zero) – must be equal to its complex conjugate H21. So then Feynman does this fantastic jump in logic. First, he keeps using the E0 value for H11 and H22, motivating that as follows: “If nature is at all reasonable, the matrix elements H11 and H22 must be equal, and we’ll call them both E0, because they correspond to the energy the states would have if H11 and H22 were zero.” Second, he uses that minus A value for H12 and H21. In short, the two equations and six functions are now reduced to:

equations

Solving these equations is rather boring. Feynman does it as follows:

solution

Now, what does these equations actually mean? It depends on those a and b coefficients. Looking at the solutions, the most obvious question to ask is: what if a or b are zero? If b is zero, then the second terms in both equations is zero, and so C1 and C2 are exactly the same: two amplitudes with the same temporal frequency ω = (E− A)/ħ. If a is zero, then C1 and C2 are the same too, but with opposite sign: two amplitudes with the same temporal frequency ω = (E+ A)/ħ. Squaring them – in both cases (i.e. for a = 0 or b = 0) – yields, once again, an equal and constant probability for the spin of the ammonia molecule to in the ‘up’ or ‘down’ or ‘down’. To be precise, we We can now take the absolute square of both to find the probability for the molecule to be in state 1 or in state 2:

  • For b = 0: |〈 1 | ψ 〉|= |(a/2)·e(i/ħ)·(E− A)·t|a2/4 = |〈 2 | ψ 〉|
  • For a = 0: |〈 1 | ψ 〉|=|(b/2)·e(i/ħ)·(E+ A)·t|= b2/4 = |〈 2 | ψ 〉|(the minus sign in front of b/2 is squared away)

So we get two stationary states now. Why two instead of one? Well… You need to use your imagination a bit here. They actually reflect each other: they’re the same as the one stationary state we found when assuming our nitrogen atom could not ‘flip’ from one position to the other. It’s just that the introduction of that possibility now results in a sort of ‘doublet’ of energy levels. But so we shouldn’t waste our time on this, as we want to analyze the general case, for which the probabilities to be in state 1 or state 2 do vary in time. So that’s when a and b are non-zero.

To analyze it all, we may want to start with equating t to zero. We then get:

C1

This leads us to conclude that a = b = 1, so our equations for C1(t) and C2(t) can now be written as:

C2

Remembering our rules for adding and subtracting complex conjugates (eiθ + e–iθ = 2cosθ and eiθ − e–iθ = 2sinθ), we can re-write this as:

C3

Now these amplitudes are much more interesting. Their temporal variation is defined by Ebut, on top of that, we have an envelope here: the cos(A·t/ħ) and sin(A·t/ħ) factor respectively. So their magnitude is no longer time-independent: both the phase as well as the amplitude now vary with time. What’s going on here becomes quite obvious when calculating and plotting the associated probabilities, which are

  • |C1(t)|= cos2(A·t/ħ), and
  • |C2(t)|= sin2(A·t/ħ)

respectively (note that the absolute square of i is equal to 1, not −1). The graph of these functions is depicted below.

graph

As Feynman puts it: “The probability sloshes back and forth.” Indeed, the way to think about this is that, if our ammonia molecule is in state 1, then it will not stay in that state. In fact, one can be sure the nitrogen atom is going to flip at some point in time, with the probabilities being defined by that fluctuating probability density function above. Indeed, as time goes by, the probability to be in state 2 increases, until it will effectively be in state 2. And then the cycle reverses.

Our | ψ 〉 = | 1 〉 C1 + | 2 〉 Cequation is a lot more interesting now, as we do have a proper mix of pure states now: we never really know in what state our molecule will be, as we have these ‘oscillating’ probabilities now, which we should interpret carefully.

The point to note is that the a = 0 and b = 0 solutions came with precise temporal frequencies: (E− A)/ħ and (E0 + A)/ħ respectively, which correspond to two separate energy levels: E− A and E0 + A respectively, with |A| = H12 = H21. So everything is related to everything once again: allowing the nitrogen atom to push its way through the three hydrogens, so as to flip to the other side, thereby breaking the energy barrier, is equivalent to associating two energy levels to the ammonia molecule as a whole, thereby introducing some uncertainty, or indefiniteness as to its energy, and that, in turn, gives us the amplitudes and probabilities that we’ve just calculated.

Note that the probabilities “sloshing back and forth”, or “dumping into each other” – as Feynman puts it – is the result of the varying magnitudes of our amplitudes, going up and down and, therefore, their absolute square varies too.

So… Well… That’s it as an introduction to a two-state system. There’s more to come. Ammonia is used in the ammonia maser. Now that is something that’s interesting to analyze—both from a classical as well as from a quantum-mechanical perspective. Feynman devotes a full chapter to it, so I’d say… Well… Have a look. 🙂

Post scriptum: I must assume this analysis of the NH3 molecule, with the nitrogen ‘flipping’ across the hydrogens, triggers a lot of questions, so let me try to answer some. Let me first insert the illustration once more, so you don’t have to scroll up:

dipole

The first thing that you should note is that the ‘flip’ involves a change in the center of mass position. So that requires energy, which is why we associate two different energy levels with the molecule: E+ A and E− A. However, as mentioned above, we don’t care about the nitty-gritty here: the energy barrier is likely to combine a number of factors, including electrostatic forces, as evidenced by the flip in the electric dipole moment, which is what the μ symbol here represents! Just note that the two energy levels are separated by an amount that’s equal to 2·A, rather than A and that, once again, it becomes obvious now why Feynman would prefer the Hamiltonian to be called the ‘energy matrix’, as its coefficients do represent specific energy levels, or differences between them! Now, that assumption yielded the following wavefunctions for C= 〈 1 | ψ 〉 and C= 〈 2 | ψ 〉:

  • C= 〈 1 | ψ 〉 = (1/2)·e(i/ħ)·(E− A)·t + (1/2)·e(i/ħ)·(E+ A)·t
  • C= 〈 2 | ψ 〉 = (1/2)·e(i/ħ)·(E− A)·t – (1/2)·e(i/ħ)·(E+ A)·t

Both are composite waves. To be precise, they are the sum of two component waves with a temporal frequency equal to ω= (E− A)/ħ and ω= (E+ A)/ħ respectively. [As for the minus sign in front of the second term in the wave equation for C2, −1 = e±iπ, so + (1/2)·e(i/ħ)·(E+ A)·t and – (1/2)·e(i/ħ)·(E+ A)·t are the same wavefunction: they only differ because their relative phase is shifted by ±π.]

Now, writing things this way, rather than in terms of probabilities, makes it clear that the two base states of the molecule themselves are associated with two different energy levels, so it is not like one state has more energy than the other. It’s just that the possibility of going from one state to the other requires an uncertainty about the energy, which is reflected by the energy doublet  E± A in the wavefunction of the base states. Now, if the wavefunction of the base states incorporates that energy doublet, then it is obvious that the state of the ammonia molecule, at any point in time, will also incorporate that energy doublet.

This triggers the following remark: what’s the uncertainty really? Is it an uncertainty in the energy, or is it an uncertainty in the wavefunction? I mean: we have a function relating the energy to a frequency. Introducing some uncertainty about the energy is mathematically equivalent to introducing uncertainty about the frequency. Think of it: two energy levels implies two frequencies, and vice versa. More in general, introducing n energy levels, or some continuous range of energy levels ΔE, amounts to saying that our wave function doesn’t have a specific frequency: it now has n frequencies, or a range of frequencies Δω = ΔE/ħ. Of course, the answer is: the uncertainty is in both, so it’s in the frequency and in the energy and both are related through the wavefunction. So… In a way, we’re chasing our own tail.

Having said that, the energy may be uncertain, but it is real. It’s there, as evidenced by the fact that the ammonia molecule behaves like an atomic oscillator: we can excite it in exactly the same way as we can excite an electron inside an atom, i.e. by shining light on it. The only difference is the photon energies: to cause a transition in an atom, we use photons in the optical or ultraviolet range, and they give us the same radiation back. To cause a transition in an ammonia molecule, we only need photons with energies in the microwave range. Here, I should quickly remind you of the frequencies and energies involved. visible light is radiation in the 400–800 terahertz range and, using the E = h·f equation, we can calculate the associated energies of a photon as 1.6 to 3.2 eV. Microwave radiation – as produced in your microwave oven – is typically in the range of 1 to 2.5 gigahertz, and the associated photon energy is 4 to 10 millionths of an eV. Having illustrated the difference in terms of the energies involved, I should add that masers and lasers are based on the same physical principle: LASER and MASER stand for Light/Micro-wave Amplification by Stimulated Emission of Radiation, respectively.

So… How shall I phrase this? There’s uncertainty, but the way we are modeling that uncertainty matters. So yes, the uncertainty in the frequency of our wavefunction and the uncertainty in the energy are mathematically equivalent, but the wavefunction has a meaning that goes much beyond that. [You may want to reflect on that yourself.]

Finally, another question you may have is why would Feynman take minus A (i.e. −A) for H12 and H21. Frankly, my first thought on this was that it should have something to do with the original equation for these Hamiltonian coefficients, which also has a minus sign: Uij(t + Δt, t) = δij + Kij(t)·Δt = δij − (i/ħ)·Hij(t)·Δt. For i ≠ j, this reduces to:

Uij(t + Δt, t) = + Kij(t)·Δt = − (i/ħ)·Hij(t)·Δt

However, the answer is: it really doesn’t matter. One could write: H12 and H21 = +A, and we’d find the same equations. We’d just switch the indices 1 and 2, and the coefficients a and b. But we get the same solutions. You can figure that out yourself. Have fun with it !

Oh ! And please do let me know if some of the stuff above would trigger other questions. I am not sure if I’ll be able to answer them, but I’ll surely try, and good question always help to ensure we sort of ‘get’ this stuff in a more intuitive way. Indeed, when everything is said and done, the goal of this blog is not simply re-produce stuff, but to truly ‘get’ it, as good as we can. 🙂