Schrödinger’s equation and the two de Broglie relations

Post scriptum note added on 11 July 2016: This is one of the more speculative posts which led to my e-publication analyzing the wavefunction as an energy propagation. With the benefit of hindsight, I would recommend you to immediately the more recent exposé on the matter that is being presented here, which you can find by clicking on the provided link. In fact, I actually made some (small) mistakes when writing the post below.

Original post:

I’ve re-visited the de Broglie equations a couple of times already. In this post, however, I want to relate them to Schrödinger’s equation. Let’s start with the de Broglie equations first. Equations. Plural. Indeed, most popularizing books on quantum physics will give you only one of the two de Broglie equations—the one that associates a wavelength (λ) with the momentum (p) of a matter-particle:

λ = h/p

In fact, even the Wikipedia article on the ‘matter wave’ starts off like that and is, therefore, very confusing, because, for a good understanding of quantum physics, one needs to realize that the λ = h/p equality is just one of a pair of two ‘matter wave’ equations:

  1. λ = h/p
  2. f = E/h

These two equations give you the spatial and temporal frequency of the wavefunction respectively. Now, those two frequencies are related – and I’ll show you how in a minute – but they are not the same. It’s like space and time: they are related, but they are definitely not the same. Now, because any wavefunction is periodic, the argument of the wavefunction – which we’ll introduce shortly – will be some angle and, hence, we’ll want to express it in radians (or – if you’re really old-fashioned – degrees). So we’ll want to express the frequency as an angular frequency (i.e. in radians per second, rather than in cycles per second), and the wavelength as a wave number (i.e. in radians per meter). Hence, you’ll usually see the two de Broglie equations written as:

  1. k = p/ħ
  2. ω = E/ħ

It’s the same: ω = 2π∙f and f = 1/T (T is the period of the oscillation), and k = 2π/λ and then ħ = h/2π, of course! [Just to remove all ambiguities: stop thinking about degrees. They’re a Babylonian legacy, who thought the numbers 6, 12, and 60 had particular religious significance. So that’s why we have twelve-hour nights and twelve-hour days, with each hour divided into sixty minutes and each minute divided into sixty seconds, and – particularly relevant in this context – why ‘once around’ is divided into 6×60 = 360 degrees. Radians are the unit in which we should measure angles because… Well… Google it. They measure an angle in distance units. That makes things easier—a lot easier! Indeed, when studying physics, the last thing you want is artificial units, like degrees.]

So… Where were we? Oh… Yes. The de Broglie relation. Popular textbooks usually commit two sins. One is that they forget to say we have two de Broglie relations, and the other one is that the E = h∙f relationship is presented as the twin of the Planck-Einstein relation for photons, which relates the energy (E) of a photon to its frequency (ν): E = h∙ν = ħ∙ω. The former is criminal neglect, I feel. As for the latter… Well… It’s true and not true: it’s incomplete, I’d say, and, therefore, also very confusing.

Why? Because both things lead one to try to relate the two equations, as momentum and energy are obviously related. In fact, I’ve wasted days, if not weeks, on this. How are they related? What formula should we use? To answer that question, we need to answer another one: what energy concept should we use? Potential energy? Kinetic energy? Should we include the equivalent energy of the rest mass?

One quickly gets into trouble here. For example, one can try the kinetic energy, K.E. = m∙v2/2, and use the definition of momentum (p = m∙v), to write E = p2/(2m), and then we could relate the frequency f to the wavelength λ using the general rule that the traveling speed of a wave is equal to the product of its wavelength and its frequency (v = λ∙f). But if E = p2/(2m) and f = v/λ, we get:

p2/(2m) = h∙v/λ ⇔  λ = 2∙h/p

So that is almost right, but not quite: that factor 2 should not be there. In fact, it’s easy to see that we’d get de Broglie’s λ = h/p equation from his E = h∙f equation if we’d use E = m∙v2 rather than E = m∙v2/2. In fact, the E = m∙v2 relation comes out of them if we just multiply the two and, yes, use that v = λ relation once again:

  1. f·λ = (E/h)·(h/p) = E/p
  2. v = λ ⇒ f·λ = v = E/p ⇔ E = v·p = v·(m·v) ⇒ E = m·v2

But… Well… E = m∙v2? How could we possibly justify the use of that formula?

The answer is simple: our v = f·λ equation is wrong. It’s just something one shouldn’t apply to the complex-valued wavefunction. The ‘correct’ velocity formula for the complex-valued wavefunction should have that 1/2 factor, so we’d write 2·f·λ = v to make things come out alright. But where would this formula come from?

Well… Now it’s time to introduce the wavefunction.

The wavefunction

You know the elementary wavefunction:

ψ = ψ(x, t) = ei(ωt − kx) = ei(kx − ωt) = cos(kx−ωt) + i∙sin(kx−ωt)

As for terminology, note that the term ‘wavefunction’ refers to what I write above, while the term ‘wave equation’ usually refers to Schrödinger’s equation, which I’ll introduce in a minute. Also note the use of boldface indicates we’re talking vectors, so we’re multiplying the wavenumber vector k with the position vector x = (x, y, z) here, although we’ll often simplify and assume one-dimensional space. In any case…

So the question is: why can’t we use the v = f·λ formula for this wave? The period of cosθ + isinθ is the same as that of the sine and cosine function considered separately: cos(θ+2π) + isin(θ+2π) = cosθ + isinθ, so T = 2π and f = 1/T = 1/2π do not change. So the f, T and λ should be the same, no?

No. We’ve got two oscillations for the price of one here: one ‘real’ and one ‘imaginary’—but both are equally essential and, hence, equally ‘real’. So we’re actually combining two waves. So it’s just like adding other waves: when adding waves, one gets a composite wave that has (a) a phase velocity and (b) a group velocity.

Huh? Yes. It’s quite interesting. When adding waves, we usually have a different ω and k for each of the component waves, and the phase and group velocity will depend on the relation between those ω’s and k’s. That relation is referred to as the dispersion relation. To be precise, if you’re adding waves, then the phase velocity of the composite wave will be equal to vp = ω/k, and its group velocity will be equal to vg = dω/dk. We’ll usually be interested in the group velocity, and so to calculate that derivative, we need to express ω as a function of k, of course, so we write ω as some function of k, i.e. ω = ω(k). There are number of possibilities then:

  1. ω and k may be directly proportional, so we can write ω as ω = a∙k: in that case, we find that vp = vg = a.
  2. ω and k are not directly proportional but have a linear relationship, so we can write write ω as ω = a∙k + b. In that case, we find that vg = a and… Well… We’ve got a problem calculating vp, because we don’t know what k to use!
  3. ω and k may be non-linearly related, in which case… Well… One does has to do the calculation and see what comes out. 🙂

Let’s now look back at our ei(kx − ωt) = cos(kx−ωt) + i∙sin(kx−ωt) function. You’ll say that we’ve got only one ω and one k here, so we’re not adding waves with different ω’s and k’s. So… Well… What?

That’s where the de Broglie equations come in. Look: k = p/ħ, and ω = E/ħ. If we now use the correct energy formula, i.e. the kinetic energy formula E = m·v2/2 (rather than that nonsensical E = m·v2 equation) – which we can also write as E = m·v·v/2 = p·v/2 = p·p/2m = p2/2m, with v = p/m the classical velocity of the elementary particle that Louis de Broglie was thinking of – then we can calculate the group velocity of our ei(kx − ωt) = cos(kx−ωt) + i∙sin(kx−ωt) as:

vg = dω/dk = d[E/ħ]/d[p/ħ] = dE/dp = d[p2/2m]/dp = 2p/2m = p/m = v

However, the phase velocity of our ei(kx − ωt) is:

vp = ω/k = (E/ħ)/(p/ħ) = E/p = (p2/2m)/p = p/2m = v/2

So that factor 1/2 only appears for the phase velocity. Weird, isn’t it? We find that the group velocity (vg) of the ei(kx − ωt) function is equal to the classical velocity of our particle (i.e. v), but that its phase velocity (vp) is equal to v divided by 2.

Hmm… What to say? Well… Nothing much—except that it makes sense, and very much so, because it’s the group velocity of the wavefunction that’s associated with the classical velocity of a particle, not the phase velocity. In fact, if we include the rest mass in our energy formula, so if we’d use the relativistic E = γm0c2 and p = γm0v formulas (with γ the Lorentz factor), then we find that vp = ω/k = E/p = (γm0c2)/(γm0v) = c2/v, and so that’s a superluminal velocity, because v is always smaller than c!

What? That’s even weirder! If we take the kinetic energy only, we find a phase velocity equal to v/2, but if we include the rest energy, then we get a superluminal phase velocity. It must be one or the other, no? Yep! You’re right! So that makes us wonder: is E = m·v2/2 really the right energy concept to use? The answer is unambiguous: no! It isn’t! And, just for the record, our young nobleman didn’t use the kinetic energy formula when he postulated his equations in his now famous PhD thesis.

So what did he use then? Where did he get his equations?

I am not sure. 🙂 A stroke of genius, it seems. According to Feynman, that’s how Schrödinger got his equation too: intuition, brilliance. In short, a stroke of genius. 🙂 Let’s relate these these two gems.

Schrödinger’s equation and the two de Broglie relations

Erwin Schrödinger and Louis de Broglie published their equations in 1924 and 1926 respectively. Can they be related? The answer is: yes—of course! Let’s first look at de Broglie‘s energy concept, however. Louis de Broglie was very familiar with Einsteins’ work and, hence, he knew that the energy of a particle consisted of three parts:

  1. The particle’s rest energy m0c2, which de Broglie referred to as internal energy (Eint): this ‘internal energy’ includes the rest mass of the ‘internal pieces’, as he put it (now we call those ‘internal pieces’ quarks), as well as their binding energy (i.e. the quarks’interaction energy);
  2. Any potential energy it may have because of some field (so de Broglie was not assuming the particle was traveling in free space), which we’ll denote by V: the field(s) can be anything—gravitational, electromagnetic—you name it: whatever changes the energy because of the position of the particle;
  3. The particle’s kinetic energy, which we wrote in terms of its momentum p: K.E. = m·v2/2 = m2·v2/(2m) = (m·v)2/(2m) = p2/(2m).

Indeed, in my previous posts, I would write the wavefunction as de Broglie wrote it, which is as follows:

ψ(θ) = ψ(x, t) = a·eiθ = a·e−i[(Eint + p2/(2m) + V)·t − p∙x]/ħ 

In those post – such as my post on virtual particles – I’d also note how a change in potential energy plays out: a change in potential energy, when moving from one place to another, would change the wavefunction, but through the momentum only—so it would impact the spatial frequency only. So the change in potential would not change the temporal frequencies ω= Eint + p12/(2m) + V1 and ω= Eint + p22/(2m) + V2. Why? Or why not, I should say? Because of the energy conservation principle—or its equivalent in quantum mechanics. The temporal frequency f or ω, i.e. the time-rate of change of the phase of the wavefunction, does not change: all of the change in potential, and the corresponding change in kinetic energy, goes into changing the spatial frequency, i.e. the wave number k or the wavelength λ, as potential energy becomes kinetic or vice versa.

So is that consistent with what we wrote above, that E = m·v2? Maybe. Let’s think about it. Let’s first look at Schrödinger’s equation in free space (i.e. a space with zero potential) once again:

Schrodinger's equation 2

If we insert our ψ = ei(kx − ωt) formula in Schrödinger’s free-space equation, we get the following nice result. [To keep things simple, we’re just assuming one-dimensional space for the calculations, so ∇2ψ = ∂2ψ/∂x2. But the result can easily be generalized.] The time derivative on the left-hand side is ∂ψ/∂t = −iω·ei(kx − ωt). The second-order derivative on the right-hand side is ∂2ψ/∂x2 = (ik)·(ik)·ei(kx − ωt) = −k2·ei(kx − ωt) . The ei(kx − ωt) factor on both sides cancels out and, hence, equating both sides gives us the following condition:

iω = −(iħ/2m)·k2 ⇔ ω = (ħ/2m)·k2

Substituting ω = E/ħ and k = p/ħ yields:

E/ħ = (ħ/2m)·p22 = m2·v2/(2m·ħ) = m·v2/(2ħ) ⇔ E = m·v2/2

Bingo! We get that kinetic energy formula! But now… What if we’d not be considering free space? In other words: what if there is some potential? Well… We’d use the complete Schrödinger equation, which is:

schrodinger 5

Huh? Why is there a minus sign now? Look carefully: I moved the iħ factor on the left-hand side to the other when writing the free space version. If we’d do that for the complete equation, we’d get:

Schrodinger's equation 3I like that representation a lot more—if only because it makes it a lot easier to interpret the equation—but, for some reason I don’t quite understand, you won’t find it like that in textbooks. Now how does it work when using the complete equation, so we add the −(i/ħ)·V·ψ term? It’s simple: the ei(kx − ωt) factor also cancels out, and so we get:

iω = −(iħ/2m)·k2−(i/ħ)·V ⇔ ω = (ħ/2m)·k+ V/ħ

Substituting ω = E/ħ and k = p/ħ once more now yields:

E/ħ = (ħ/2m)·p22 + V/ħ = m2·v2/(2m·ħ) + V/ħ = m·v2/(2ħ) + V/ħ ⇔ E = m·v2/2 + V

Bingo once more!

The only thing that’s missing now is the particle’s rest energy m0c2, which de Broglie referred to as internal energy (Eint). That includes everything, i.e. not only the rest mass of the ‘internal pieces’ (as said, now we call those ‘internal pieces’ quarks) but also their binding energy (i.e. the quarks’interaction energy). So how do we get that energy concept out of Schrödinger’s equation? There’s only one answer to that: that energy is just like V. We can, quite simply, just add it.

That brings us to the last and final question: what about our vg = result if we do not use the kinetic energy concept, but the E = m·v2/2 + V + Eint concept? The answer is simple: nothing. We still get the same, because we’re taking a derivative and the V and Eint just appear as constants, and so their derivative with respect to p is zero. Check it:

vg = dω/dk = d[E/ħ]/d[p/ħ] = dE/dp = d[p2/2m + V + Eint ]/dp = 2p/2m = p/m = v

It’s now pretty clear how this thing works. To localize our particle, we just superimpose a zillion of these ei(ωt − kx) equations. The only condition is that we’ve got that fixed vg = dω/dk = v relationhip, but so we do have such fixed relationship—as you can see above. In fact, the Wikipedia article on the dispersion relation mentions that the de Broglie equations imply the following relation between ω and k: ω = ħk2/2m. As you can see, that’s not entirely correct: the author conveniently forgets the potential (V) and the rest energy (Eint) in the energy formula here!

What about the phase velocity? That’s a different story altogether. You can think about that for yourself. 🙂

I should make one final point here. As said, in order to localize a particle (or, to be precise, its wavefunction), we’re going to add a zillion elementary wavefunctions, each of which will make its own contribution to the composite wave. That contribution is captured by some coefficient ai in front of every eiθi function, so we’ll have a zillion aieiθi functions, really. [Yep. Bit confusing: I use here as subscript, as well as imaginary unit.] In case you wonder how that works out with Schrödinger’s equation, the answer is – once again – very simple: both the time derivative (which is just a first-order derivative) and the Laplacian are linear operators, so Schrödinger’s equation, for a composite wave, can just be re-written as the sum of a zillion ‘elementary’ wave equations.

So… Well… We’re all set now to effectively use Schrödinger’s equation to calculate the orbitals for a hydrogen atom, which is what we’ll do in our next post.

In the meanwhile, you can amuse yourself with reading a nice Wikibook article on the Laplacian, which gives you a nice feel for what Schrödinger’s equation actually represents—even if I gave you a good feel for that too on my Essentials page. Whatever. You choose. Just let me know what you liked best. 🙂

Oh… One more point: the vg = dω/dk = d[p2/2m]/dp = p/m = calculation obviously assumes we can treat m as a constant. In fact, what we’re actually doing is a rather complicated substitution of variables: you should write it all out—but that’s not the point here. The point is that we’re actually doing a non-relativistic calculation. Now, that does not mean that the wavefunction isn’t consistent with special relativity. It is. In fact, in one of my posts, I show how we can explain relativistic length contraction using the wavefunction. But it does mean that our calculation of the group velocity is not relativistically correct. But that’s a minor point: I’ll leave it for you as an exercise to calculate the relativistically correct formula for the group velocity. Have fun with it! 🙂

Note: Notations are often quite confusing. One should, generally speaking, denote a frequency by ν (nu), rather than by f, so as to not cause confusion with any function f, but then… Well… You create a new problem when you do that, because that Greek letter nu (ν) looks damn similar to the v of velocity, so that’s why I’ll often use f when I should be using nu (ν). As for the units, a frequency is expressed in cycles per second, while the angular frequency ω is expressed in radians per second. One cycle covers 2π radians and, therefore, we can write: ν = ω/2π. Hence, h∙ν = h∙ω/2π = ħ∙ω. Both ν as well as ω measure the time-rate of change of the phase of the wave function, as opposed to k, i.e. the spatial frequency of the wave function, which depends on the speed of the wave. Physicists also often use the symbol v for the speed of a wave, which is also hugely confusing, because it’s also used to denote the classical velocity of the particle. And then there’s two wave velocities, of course: the group versus the phase velocity. In any case… I find the use of that other symbol (c) for the wave velocity even more confusing, because this symbol is also used for the speed of light, and the speed of a wave is not necessarily (read: usually not) equal to the speed of light. In fact, both the group as well as the phase velocity of a particle wave are very different from the speed of light. The speed of a wave and the speed of light only coincide for electromagnetic waves and, even then, it should be noted that photons also have amplitudes to travel faster or slower than the speed of light.

Re-visiting the matter wave (I)

In my previous posts, I introduced a lot of wave formulas. They are essential to understanding waves – both real ones (e.g. electromagnetic waves) as well as probability amplitude functions. Probability amplitude function is quite a mouthful so let me call it a matter wave, or a de Broglie wave. The formulas are necessary to create true understanding – whatever that means to you – because otherwise we just keep on repeating very simplistic but nonsensical things such as ‘matter behaves (sometimes) like light’, ‘light behaves (sometimes) like matter’ or, combining both, ‘light and matter behave like wavicles’. Indeed: what does ‘like‘ mean? Like the same but different? 🙂 So that means it’s different. Let’s therefore re-visit the matter wave (i.e. the de Broglie wave) and point out the differences with light waves.

In fact, this post actually has its origin in a mistake in a post scriptum of a previous post (An Easy Piece: On Quantum Mechanics and the Wave Function), in which I wondered what formula to use for the energy E in the (first) de Broglie relation E = hf (with the frequency of the matter wave and h the Planck constant). Should we use (a) the kinetic energy of the particle, (b) the rest mass (mass is energy, remember?), or (c) its total energy? So let us first re-visit these de Broglie relations which, you’ll remember, relate energy and momentum to frequency (f) and wavelength (λ) respectively with the Planck constant as the factor of proportionality:

E = hf and p = h/λ

The de Broglie wave

I first tried kinetic energy in that E = h equation. However, if you use the kinetic energy formula (K.E. = mv2/2, with the velocity of the particle), then the second de Broglie relation (p = h/λ) does not come out right. The second de Broglie relation has the wavelength λ on the right side, not the frequency f. But it’s easy to go from one to the other: frequency and wavelength are related through the velocity of the wave (v). Indeed, the number of cycles per second (i.e. the frequency f) times the length of one cycle (i.e. the wavelength λ) gives the distance traveled by the wave per second, i.e. its velocity v. So fλ = v. Hence, using that kinetic energy formula and that very obvious fλ = v relation, we can write E = hf as mv2/2 = v/λ and, hence, after moving one of the two v’s in v2 (and the 1/2 factor) on the left side to the right side of this equation, we get mv = 2h/λ. So there we are:

p = mv = 2h/λ.

Well… No. The second de Broglie relation is just p = h/λ. There is no factor 2 in it. So what’s wrong?

A factor of 2 in an equation like this surely doesn’t matter, does it? It does. We are talking tiny wavelengths here but a wavelength of 1 nanometer (1×10–9 m) – this is just an example of the scale we’re talking about here – is not the same as a wavelength of 0.5 nm. There’s another problem too. Let’s go back to our an example of an electron with a mass of 9.1×10–31 kg (that’s very tiny, and so you’ll usually see it expressed in a unit that’s more appropriate to the atomic scale), moving about with a velocity of 2.2×106 m/s (that’s the estimated speed of orbit of an electron around a hydrogen nucleus: it’s fast (2,200 km per second), but still less than 1% of the speed of light), and let’s do the math. 

[Before I do the math, however, let me quickly insert a line on that ‘other unit’ to measure mass. You will usually see it written down as eV, so that’s electronvolt. Electronvolt is a measure of energy but that’s OK because mass is energy according to Einstein’s mass-energy equation: E = mc2. The point to note is that the actual measure for mass at the atomic scale is eV/c2, so we make the unit even smaller by dividing the eV (which already is a very tiny amount of energy) by c2: 1 eV/ccorresponds to 1.782662×10−36 kg, so the mass of our electron (9.1×10–31 kg) is about 510,000 eV/c2, or 0.510 MeV/c2. I am spelling it out because you will often just see 0.510 MeV in older or more popular publications, but so don’t forget that cfactor. As for the calculations below, I just stick to the kg and m measures because they make the dimensions come out right.]

According to our kinetic energy formula (K.E. = mv2/2), these mass and velocity values correspond to an energy value of 22 ×10−19 Joule (the Joule is the so-called SI unit for energy – don’t worry about it right now). So, from the first de Broglie equation (f = E/h) – and using the right value for Planck’s constant (6.626 J·s), we get a frequency of 3.32×1015 hertz (hertz just means oscillations per second as you know). Now, using v once again, and fλ = v, we see that corresponds to a wavelength of 0.66 nanometer (0.66×10−9 m). [Just take the numbers and do the math.] 

However, if we use the second de Broglie relation, which relates wavelength to momentum instead of energy, then we get 0.33 nanometer (0.33×10−9 m), so that’s half of the value we got from the first equation. So what is it: 0.33 or 0.66 nm? It’s that factor 2 again. Something is wrong.

It must be that kinetic energy formula. You’ll say we should include potential energy or something. No. That’s not the issue. First, we’re talking a free particle here: an electron moving in space (a vacuum) with no external forces acting on it, so it’s a field-free space (or a region of constant potential). Second, we could, of course, extend the analysis and include potential energy, and show how it’s converted to kinetic energy (like a stone falling from 100 m to 50 m: potential energy gets converted into kinetic energy) but making our analysis more complicated by including potential energy as well will not solve our problem here: it will only make you even more confused.

Then it must be some relativistic effect you’ll say. No. It’s true the formula for kinetic energy above only holds for relatively low speeds (as compared to light, so ‘relatively’ low can be thousands of km per second) but that’s not the problem here: we are talking electrons moving at non-relativistic speeds indeed, so their mass or energy is not (or hardly) affected by relativistic effects and, hence, we can indeed use the more simple non-relativistic formulas.

The real problem we’re encountering here is not with the equations: it’s the simplistic model of our wave. We are imagining one wave here indeed, with a single frequency, a single wavelength and, hence, one single velocity – which happens to coincide with the velocity of our particle. Such wave cannot possibly represent an actual de Broglie wave: the wave is everywhere and, hence, the particle it represents is nowhere. Indeed, a wave defined by a specific wavelength λ (or a wave number k = 2π/λ if we’re using complex number notation) and a specific frequency f or period T (or angular frequency ω = 2π/T = 2πf) will have a very regular shape – such as Ψ = Aei(ωt-kx) and, hence, the probability of actually locating that particle at some specific point in space will be the same everywhere: |Ψ|= |Aei(ωt-kx)|= A2. [If you are confused about the math here, I am sorry but I cannot re-explain this once again: just remember that our de Broglie wave represents probability amplitudes – so that’s some complex number Ψ = Ψ(x, t) depending on space and time – and that we  need to take the modulus squared of that complex number to get the probability associated with some (real) value x (i.e. the space variable) and some value t (i.e. the time variable).]

So the actual matter wave of a real-life electron will be represented by a wave train, or a wave packet as it is usually referred to. Now, a wave packet is described by (at least) two types of wave velocity:

  1. The so-called group velocity: the group velocity of a wave is denoted by vand is the velocity of the wave packet as a whole is traveling. Wikipedia defines it as “the velocity with which the overall shape of the waves’ amplitudes — known as the modulation or envelope of the wave — propagates through space.”
  2. The so-called phase velocity: the phase velocity is denoted by vp and is what we usually associate with the velocity of a wave. It is just what it says it is: the rate at which the phase of the (composite) wave travels through space.

The term between brackets above – ‘composite’ – already indicates what it’s all about: a wave packet is to be analyzed as a composite wave: so it’s a wave composed of a finite or infinite number of component waves which all have their own wave number k and their own angular frequency ω. So the mistake we made above is that, naively, we just assumed that (i) there is only one simple wave (and, of course, there is only one wave, but it’s not a simple one: it’s a composite wave), and (ii) that the velocity v of our electron would be equal to the velocity of that wave. Now that we are a little bit more enlightened, we need to answer two questions in regard to point (ii):

  1. Why would that be the case?
  2. If it’s is the case, then what wave velocity are we talking about: the group velocity or the phase velocity?

To answer both questions, we need to look at wave packets once again, so let’s do that. Just to visualize things, I’ll insert – once more – that illustration you’ve seen in my other posts already:

Explanation of uncertainty principle

The de Broglie wave packet

The Wikipedia article on the group velocity of a wave has wonderful animations, which I would advise you to look at in order to make sure you are following me here. There are several possibilities:

  1. The phase velocity and the group velocity are the same: that’s a rather unexciting possibility but it’s the easiest thing to work with and, hence, most examples will assume that this is the case.
  2. The group and phase velocity are not the same, but our wave packet is ‘stable’, so to say. In other words, the individual peaks and troughs of the wave within the envelope travel at a different speed (the phase velocity vg), but the envelope as a whole (so the wave packet as such) does not get distorted as it travels through space.
  3. The wave packet dissipates: in this case, we have a constant group velocity, but the wave packet delocalizes. Its width increases over time and so the wave packet diffuses – as time goes by – over a wider and wider region of space, until it’s actually no longer there. [In case you wonder why it did not group this third possibility under (2): it’s a bit difficult to assign a fixed phase velocity to a wave like this.]

How the wave packet will behave depends on the characteristics of the component waves. To be precise, it will depend on their angular frequency and their wave number and, hence, their individual velocities. First, note the relationship between these three variables: ω = 2πf and k = 2π/λ so ω/k = fλ = v. So these variables are not independent: if you have two values (e.g. v and k), you also have the third one (ω). Secondly, note that the component waves of our wave packet will have different wavelengths and, hence, different wave numbers k.

Now, the de Broglie relation p = ħk (i.e. the same relation as p = h/λ but we replace λ with 2π/k and then ħ is the so-called reduced Planck constant ħ = h/2π) makes it obvious that different wave numbers k correspond to different values p for the momentum of our electron, so allowing for a spread in k (or a spread in λ as illustrates above) amounts to allowing for some spread in p. That’s where the uncertainty principle comes in – which I actually derived from a theoretical wave function in my post on Fourier transforms and conjugate variables. But so that’s not something I want to dwell on here.

We’re interested in the ω’s. What about them? Well… ω can take any value really – from a theoretical point of view that is. Now you’ll surely object to that from a practical point of view, because you know what it implies: different velocities of the component waves. But you can’t object in a theoretical analysis like this. The only thing we could possible impose as a constraint is that our wave packet should not dissipate – so we don’t want it to delocalize and/or vanish after a while because we’re talking about some real-life electron here, and so that’s a particle which just doesn’t vanish like that.

To impose that condition, we need to look at the so-called dispersion relation. We know that we’ll have a whole range of wave numbers k, but so what values should ω take for a wave function to be ‘well-behaved’, i.e. not disperse in our case? Let’s first accept that k is some variable, the independent variable actually, and so then we associate some ω with each of these values k. So ω becomes the dependent variable (dependent on k that is) and that amounts to saying that we have some function ω = ω(k).

What kind of function? Well… It’s called the dispersion relation – for rather obvious reasons: because this function determines how the wave packet will behave: non-dispersive or – what we don’t want here – dispersive. Indeed, there are several possibilities:

  1. The speed of all component waves is the same: that means that the ratio ω/k = is the same for all component waves. Now that’s the case only if ω is directly proportional to k, with the factor of proportionality equal to v. That means that we have a very simple dispersion relation: ω = αk with α some constant equal to the velocity of the component waves as well as the group and phase velocity of the composite wave. So all velocities are just the same (vvp = vg = α) and we’re in the first of the three cases explained at the beginning of this section.
  2. There is a linear relation between ω and k but no direct proportionality, so we write ω = αk + β, in which β can be anything but not some function of k. So we allow different wave speeds for the component waves. The phase velocity will, once again, be equal to the ratio of the angular frequency and the wave number of the composite wave (whatever that is), but what about the group velocity, i.e. the velocity of our electron in this example? Well… One can show – but I will not do it here because it is quite a bit of work – that the group velocity of the wave packet will be equal to vg = dω/dk, i.e. the (first-order) derivative of ω with respect to k. So, if we want that wave packet to travel at the same speed of our electron (which is what we want of course because, otherwise, the wave packet would obviously not represent our electron), we’ll have to impose that dω/dk (or ∂ω/∂k if you would want to introduce more independent variables) equals v. In short, we have the condition that dω/dk = d(αk + β)/dk = α = k.
  3. If the relation between ω and k is non-linear, well… Then we have none of the above. Hence, we then have a wave packet that gets distorted and stretched out and actually vanishes after a while. That case surely does not represent an electron.

Back to the de Broglie wave relations

Indeed, it’s now time to go back to our de Broglie relations – E = hf and p = h/λ and the question that sparked the presentation above: what formula to use for E? Indeed, for p it’s easy: we use p = mv and, if you want to include the case of relativistic speeds, you will write that formula in a more sophisticated way by making it explicit that the mass m is the relativistic mass m = γm0: the rest mass multiplied with a factor referred to as the Lorentz factor which, I am sure, you have seen before: γ = (1 – v2/c2)–1/2. At relativistic speeds (i.e. speeds close to c), this factor makes a difference: it adds mass to the rest mass. So the mass of a particle can be written as m = γm0, with m0 denoting the rest mass. At low speeds (e.g. 1% of the speed of light – as in the case of our electron), m will hardly differ from m0 and then we don’t need this Lorentz factor. It only comes into play at higher speeds.

At this point, I just can’t resist a small digression. It’s just to show that it’s not ‘relativistic effects’ that cause us trouble in finding the right energy equation for our E = hf relation. What’s kinetic energy? Well… There’s a few definitions – such as the energy gathered through converting potential energy – but one very useful definition in the current context is the following: kinetic energy is the excess of a particle over its rest mass energy. So when we’re looking at high-speed or high-energy particles, we will write the kinetic energy as K.E. = mc– m0c= (m – m0)c= γm0c– m0c= m0c2(γ – 1). Before you think I am trying to cheat you: where is the v of our particle? [To make it specific: think about our electron once again but not moving at leisure this time around: imagine it’s speeding at a velocity very close to c in some particle accelerator. Now, v is close to c but not equal to c and so it should not disappear. […]

It’s in the Lorentz factor γ = (1 – v2/c2)–1/2.

Now, we can expand γ into a binomial series (it’s basically an application of the Taylor series – but just check it online if you’re in doubt), so we can write γ as an infinite sum of the following terms: γ = 1 + (1/2)·v2/c+ (3/8)·v4/c+ (3/8)·v4/c+ (5/16)·v6/c+ … etcetera. [The binomial series is an infinite Taylor series, so it’s not to be confused with the (finite) binomial expansion.] Now, when we plug this back into our (relativistic) kinetic energy equation, we can scrap a few things (just do it) to get where I want to get:

K.E. = (1/2)·m0v+ (3/8)·m0v4/c+ (5/16)·m0v6/c+ … etcetera

So what? Well… That’s it – for the digression at least: see how our non-relativistic formula for kinetic energy (K.E. = m0v2/2 is only the first term of this series and, hence, just an approximation: at low speeds, the second, third etcetera terms represent close to nothing (and more close to nothing as you check out the fourth, fifth etcetera terms). OK, OK… You’re getting tired of these games. So what? Should we use this relativistic kinetic energy formula in the de Broglie relation?

No. As mentioned above already, we don’t need any relativistic correction, but the relativistic formula above does come in handy to understand the next bit. What’s the next bit about?

Well… It turns out that we actually do have to use the total energy – including (the energy equivalent to) the rest mass of our electron – in the de Broglie relation E = hf.

WHAT!?

If you think a few seconds about the math of this – so we’d use γm0c2 instead of (1/2)m0v2 (so we use the speed of light instead of the speed of our particle) – you’ll realize we’ll be getting some astronomical frequency (we got that already but so here we are talking some kind of truly fantastic frequency) and, hence, combining that with the wavelength we’d derive from the other de Broglie equation (p = h/λ) we’d surely get some kind of totally unreal speed. Whatever it is, it will surely have nothing to do with our electron, does it?

Let’s go through the math.

The wavelength is just the same as that one given by p = h/λ, so we have λ = 0.33 nanometer. Don’t worry about this. That’s what it is indeed. Check it out online: it’s about a thousand times smaller than the wavelength of (visible) light but that’s OK. We’re talking something real here. That’s why electron microscopes can ‘see’ stuff that light microscopes can’t: their resolution is about a thousand times higher indeed.

But so when we take the first equation once again (E =hf) and calculate the frequency from f = γm0c2/h, we get an frequency in the neighborhood of 12.34×1019 herz. So that gives a velocity of v = fλ = 4.1×1010 meter per second (m/s). But… THAT’S MORE THAN A HUNDRED TIMES THE SPEED OF LIGHT. Surely, we must have got it wrong.

We don’t. The velocity we are calculating here is the phase velocity vp of our matter wave – and IT’S REAL! More in general, it’s easy to show that this phase velocity is equal to vp = fλ = E/p = (γm0c2/h)·(h/γm0v) = c2/v. Just fill in the values for c and v (3×108 and 2.2×106 respectively and you will get the same answer.

But that’s not consistent with relativity, is it? It is: phase velocities can be (and, in fact, usually are – as evidenced by our real-life example) superluminal as they say – i.e. much higher than the speed of light. However, because they carry no information – the wave packet shape is the ‘information’, i.e. the (approximate) location of our electron – such phase velocities do not conflict with relativity theory. It’s like amplitude modulation, like AM radiowaves): the modulation of the amplitude carries the signal, not the carrier wave.

The group velocity, on the other hand, can obviously not be faster than and, in fact, should be equal to the speed of our particle (i.e. the electron). So how do we calculate that? We don’t have any formula ω(k) here, do we? No. But we don’t need one. Indeed, we can write:

v= ∂ω/∂k = ∂(E/ ħ)/∂(p/ ħ) = ∂E/∂p

[Do you see why we prefer the ∂ symbol instead of the d symbol now? ω is a function of k but it’s – first and foremost – a function of E, so a partial derivative sign is quite appropriate.]

So what? Well… Now you can use either the relativistic or non-relativistic relation between E and p to get a value for ∂E/∂p. Let’s take the non-relativistic one first (E = p2/2m) : ∂E/∂p = ∂(p2/2m)/∂p = p/m = v. So we get the velocity of our electron! Just like we wanted. 🙂 As for the relativistic formula (E = (p2c+ m02c4)1/2), well… I’ll let you figure that one out yourself. [You can also find it online in case you’d be desperate.]

Wow! So there we are. That was quite something! I will let you digest this for now. It’s true I promised to ‘point out the differences between matter waves and light waves’ in my introduction but this post has been lengthy enough. I’ll save those ‘differences’ for the next post. In the meanwhile, I hope you enjoyed and – more importantly – understood this one. If you did, you’re a master! A real one! 🙂