LST Relation – The Physical Picture

In 1941, Lydanne, Sachs and Teller wrote a paper entitled “On the Polar Vibrations of Alkali Halides”, where they derived a result now known as the Lydanne-Sachs-Teller (LST) relation. It has wide applicability for polar insulators. I reproduce the relation below:

\frac{\omega_{LO}^2}{\omega_{TO}^2} = \frac{\epsilon(o)}{\epsilon(\infty)}

In the equation above, \omega_{LO} and \omega_{TO} refer to the frequencies of the longitudinal and transverse optical phonons respectively. \epsilon(0) and \epsilon(\infty) refer to the static and high frequency (above the phonon frequencies, but below any electronic energy scale) dielectric constants. All these quantities are understood to be the values in the long-wavelength limit (i.e. q \approx 0).

The beautiful thing about the LST result is that it is independent of any microscopic description, which is quite unusual in solid-state physics. Therefore, the result can be derived from classical electrodynamics, without resorting to any quantum mechanics. It is an interesting question as to whether or not quantum mechanics plays a role in the long-wavelength optical response in general.

Regardless, it turns out that all quantities in the LST relation are experimentally accessible! I find this relation quite remarkable and deep. Not only that, the agreement with experiment in many polar semiconductors is excellent. Take a look at the table below to get an idea of how well this relation holds for a few materials (reproduced from Mark Fox’s textbook Optical Properties of Solids):lstrelation

I have found textbook derivations don’t give a good intuition of why this relation holds, so here is my attempt to rectify this situation. First, let me state an important assumption that goes into the LST relation:

The phonons are assumed to be in the harmonic limit (i.e. no phonon anharmonicity) and as a result, the dielectric constant has the following form:

\epsilon(\omega) = \epsilon(\infty) + \frac{C}{\omega_{TO}^2-\omega^2}

where C is a constant. This form of the dielectric constant can be arrived at using either classical electrodynamics or quantum mechanics (see e.g. Ashcroft and Mermin, Kittel or Ziman).

Now, with this result under our belts, it turns out that it is quite simple to understand why the LST relation holds. In a simple polar semiconductor, we have two atoms per unit cell that are oppositely charged like so:

Therefore, for the longitudinal optical phonon we have an extra polarization effect due to the long-range nature of the Coulomb interaction. This extra polarization results in an extra restoring force (in addition to the springy restoring force between the ions), yielding a higher longitudinal phonon frequency compared to the transverse optical phonon. I have discussed this a little more extensively in a previous post. This extra restoring force (which is only present for the longitudinal oscillation) is pictured below:


The longitudinal optical phonon is at a higher energy because of the extra Coulombic polarization effect

More precisely, we can write the following when including this extra restoring force:

\omega_{LO}^2 = \omega_{TO}^2 + \frac{C}{\epsilon(\infty)}

There is an \epsilon(\infty) in the formula above because this polarization will necessarily be screened by higher energy (electronic) processes. Dividing both sides by \omega_{TO}^2, we can write the above equation suggestively as:

\frac{\omega_{LO}^2}{\omega_{TO}^2} = \frac{\epsilon(\infty)+C/\omega_{TO}^2}{\epsilon(\infty)}

Looking at the equation for the dielectric constant from earlier, this is precisely the LST relation! In effect, the same extra restoring due to the long-range Coulomb interaction leads to the extra screening in the static limit, yielding, in my mind, a delightful little result.

Using the LST relation, we can deduce a property of ferroelectric materials. Namely, we know that at the transition temperature between the normal state and a ferroelectric ground state, the static dielectric constant, \epsilon(0), diverges. Therefore, we can surmise from the LST relation that a zone center transverse optical phonon must go to zero energy (soften) at the transition temperature (see here for PbTiO3). This is a totally non-trivial consequence of the LST relation, demonstrating again its far-reaching utility.

Did I mention that I think this result is pretty excellent?

I’d like to acknowledge Zhanybek Alpichshev for enlightening some aspects regarding this topic.

Too Close to Home

I haven’t been blogging much recently because I just moved from Chicago to Boston. Also, I don’t currently have access to internet in my new apartment. As always, there’s an XKCD comic to capture this scenario:


Hopefully, I’ll be back and posting more often soon!

An Interesting Research Avenue, an Update, and a Joke

An Interesting Research Avenue: A couple months ago, Stephane Mangin of the Insitut Jean Lamour gave a talk on all-optical helicity-dependent magnetic switching (what a mouthful!) at Argonne, which was fascinating. I was reminded of the talk yesterday when a review article on the topic appeared on the arXiv. The basic phenomenon is that in certain materials, one is able to send in a femtosecond laser pulse onto a magnetic material and switch the direction of magnetization using circularly polarized light. This effect is reversible (in the sense that circularly polarized light in the opposite direction will result in a magnetization in the opposite direction) and is reproducible. During the talk, Mangin was able to show us some remarkable videos of the phenomenon, which unfortunately, I wasn’t able to find online.

The initial study that sparked a lot of this work was this paper by Beaurepaire et al., which showed ultrafast demagnetization in nickel films in 1996, a whole 20 years ago! The more recent study that triggered most of the current work was this paper by Stanciu et al. in which it was shown that the magnetization direction could be switched with a circularly polarized 40-femtosecond laser pulse on ferromagnetic film alloys of GdFeCo. For a while, it was thought that this effect was specific to the GdFeCo material class, but it has since been shown that all-optical helicity-dependent magnetic switching is actually a more general phenomenon and has been observed now in many materials (see this paper by Mangin and co-workers for example). It will be interesting to see how this research plays out with respect to the magnetic storage industry. The ability to read and write on the femtosecond to picosecond timescale is definitely something to watch out for.

Update: After my post on the Gibbs paradox last week, a few readers pointed out that there exists some controversy over the textbook explanation that I presented. I am grateful that they provided links to some articles discussing the subtleties involved in the paradox. Although one commenter suggested Appendix D of E. Atlee Jackson’s textbook, I was not able to get a hold of this. It looks like a promising textbook, so I may end up just buying it, however!

The links that I found helpful about the Gibbs paradox were Jaynes’ article (pdf!) and this article by R. Swendsen. In particular, I found Jaynes’ discussion of Whifnium and Whoofnium interesting in the role that ignorance and knowledge plays our ability to extract work from a partitioned gases. Swendsen’s tries to redefine entropy classically (what he calls Boltzmann’s definition of entropy), which I have to think about a little more. But at the moment, I don’t think I buy his argument that this resolves the Gibbs paradox completely.

A Joke: 

Q: What did Mrs. Cow say to Mr. Cow?

A: Hubby, could you please mooo the lawn?

Q: What did Mr. Cow say back to Mrs. Cow?

A: But, sweetheart, then what am I going to eat?

Gibbs Paradox and Epicycles

Thomas Kuhn, the famous philosopher of science, envisioned that scientific revolutions take place when “an increasing number of epicycles” arise, resulting in the untenability of a prevailing theory. Just in case you aren’t familiar, the “epicycles” are a reference to the Ptolemaic world-view with the earth at the center of the universe. To explain the trajectories of the other planets, Ptolemaic theory required that the planets circulate the earth in complicated trajectories called epicycles. These convoluted epicycles were no longer needed once the Copernican revolution took place, and it was realized that our solar system was heliocentric.

This post is specifically about the Gibbs paradox, which provided one of the first examples of an “epicycle” in classical mechanics. If you google Gibbs paradox, you will come up with several different explanations, which are all seemingly related, but don’t quite all tell the same story. So instead of following Gibbs’ original arguments, I’ll just go by the version which is the easiest (in my mind) to follow.

Imagine a large box that is partitioned in two, with volume V on either side, filled with helium gas of the same pressure, temperature, etc. and at equilibrium (i.e. the gases are identical). The total entropy in this scenario is S + S =2S. Now, imagine that the partition is removed. The question Gibbs asked himself was: does the entropy increase?

Now, from our perspective, this might seems like an almost silly question, but Gibbs had asked himself this question in 1875, before the advent of quantum mechanics. This is relevant because in classical mechanics, particles are always distinguishable (i.e. they can be “tagged” by their trajectories). Hence, if one calculates the entropy increase assuming distinguishable particles, one gets the result that the entropy increases by 2Nk\textrm{ln}2.

This is totally at odds with one’s intuition (if one has any intuition when it comes to entropy!) and the extensive nature of entropy (that entropy scales with the system size). Since the size of the larger container of volume 2V containing identical gases (i.e. same pressure and temperature) does not change when removing the partition, neither should the entropy. And most damningly, if one were to place the partition back where it was before, one would naively think that the entropy would return to 2S, suggesting that the entropy decreased when returning the partition.

The resolution to this paradox is that the particles (helium atoms in this case) are completely indistinguishable. Gibbs had indeed recognized this as the resolution to the problem at the time, but considered it a counting problem.

Little did he know that the seeds giving rise to this seemingly benign problem required the complete overthrow of classical mechanics in favor of quantum mechanics. Only in quantum mechanics do truly identical particles exist. Note that nowhere in the Gibbs paradox does it suggest what the next theory will look like – it only points out a severe shortcoming of classical mechanics. Looked at in this light, it is amusing to think about what sorts of epicycles are hiding within our seemingly unshakable theories of quantum mechanics and general relativity, perhaps even in plain sight.

Lunar Eclipse and the 22 Degree Halo

The beautiful thing about atmospheric optics is that (almost) everyone can look up at the sky and see stunning optical phenomena from the sun, moon or some other celestial object. In this post I’ll focus on two particularly striking phenomena where the physical essence can be captured with relatively simple explanations.

The 22 degree halo is a ring around the sun or moon, which is often observed on cold days. Here are a couple images of the 22 degree halo around the sun and moon respectively:


22 degree halo around the sun


22 degree halo around the moon

Note that the 22 degree halo is distinct from the coronae, which occur due to different reasons. While the coronae arise due to the presence of water droplets, the 22 degree halo arises specifically due to the presence of hexagonal ice crystals in the earth’s atmosphere. So why 22 degrees? Well, it turns out that one can answer the question using rather simple undergraduate-level physics. One of the most famous questions in undergraduate optics is that of light refraction through a prism, illustrated below:


Fig. 1: The Snell’s Law Prism Problem

But if there were hexagonal ice crystals in the atmosphere, the problem is exactly the same, as one can see below. This is so because a hexagon is just an equilateral triangle with its ends chopped off. So as long as the light enters and exits on two sides of the hexagon that are spaced one side apart, the analysis is the same as for the triangle.


Equilateral triangle with ends chopped off, making a hexagon

It turns out that \theta_4 in Fig. 1 can be solved as a function of \theta_1 with Snell’s law and some simple trigonometry to yield (under the assumption that n_1 =1):

\theta_4 = \textrm{sin}^{-1}(n_2 \times \textrm{sin}(60-\textrm{sin}^{-1}(\textrm{sin}(\theta_1)/n_2)))

It is then pretty straightforward to obtain \delta, the difference in angle between the incident and refracted beam as a function of \theta_1. I have plotted this below for the index of refraction of ice crystals for three different colors of light, red, green and blue (n_2 = 1.306, 1.311 and 1.317 respectively):


The important thing to note in the plot above is that there is a minimum angle below which there is no refracted beam, and this angle is precisely 21.54, 21.92 and 22.37 degrees for red, green and blue light respectively. Because there is no refracted beam below 22 degrees, this region appears darker, and then there is a sudden appearance of the refracted beam at the angles listed above. This is what gives rise to the 22 degree halo and also to the reddish hue on the inside rim of the halo.

Another rather spectacular celestial occurrence is the lunar eclipse, where the earth completely obscures the moon from direct sunlight. This is the geometry for the lunar eclipse:


Geometry of the lunar eclipse

The question I wanted to address is the reddish hue of the moon, despite it lying in the earth’s shadow. It would naively seem like the moon should not be observable at all. However, there is a similar effect occurring here as with the halo. In this case, the earth’s atmosphere is the refracting medium. So just as light incident on the prism was going upward and then exited going downward, the sun’s rays similarly enter the atmosphere on a trajectory that would miss the moon, but then are bent towards the moon after interacting with the earth’s atmosphere.

But why red? Well, this has the same origins as the reddish hue of the sunset. Because light scatters from atmospheric particles as 1/\lambda^4, blue light gets scattered away much more easily than red light. Hence, the only color of light left by the time the light reaches the moon is primarily of red color.

It is interesting to imagine what the earth looks like from the moon during a lunar eclipse — it likely looks completely dark apart from a spectacular red halo around the earth. Anyway, one should realize that Snell’s law was first formulated in 984 by Arab scientist Ibn Sahl, and so it was possible to come to these conclusions more than a thousand years ago. Nothing new here!

Precision in Many-Body Systems

Measurements of the quantum Hall effect give a precise conductance in units of e^2/h. Measurements of the frequency of the AC current in a Josephson junction give us a frequency of 2e/h times the applied voltage. Hydrodynamic circulation in liquid 4He is quantized in units of h/m_{4He}. These measurements (and similar ones like flux quantization) are remarkable. They yield fundamental constants to a great degree of accuracy in a condensed matter setting– a setting which Murray Gell-Mann once referred to as “squalid state” systems. How is this possible?

At first sight, it is stunning that physics of the solid or liquid state could yield a measurement so precise. When we consider the defects, impurities, surfaces and other imperfections in a macroscopic system, these results become even more astounding.

So where does this precision come from? It turns out that in all cases, one is measuring a quantity that is dependent on the single-valued nature of the (appropriately defined) complex scalar  wavefunction. The aforementioned quantities are measured in integer units, n, usually referred to as the winding number. Because the winding number is a topological quantity, in the sense that it arises in a multiply-connected space, these measurements do not particularly care about the small differences that occur in its surroundings.

For instance, the leads used to measure the quantum Hall effect can be placed virtually anywhere on the sample, as long as the wires don’t cross each other. The samples can be any (two-dimensional) geometry, i.e. a square, a circle or some complicated corrugated object. In the Josephson case, the weak links can be constrictions, an insulating oxide layer, a metal, etc. Imprecision of experimental setup is not detrimental, as long as the experimental geometry remains the same.

Another ingredient that is required for this precision is a large number of particles. This can seem counter-intuitive, since one expects quantization on a microscopic rather than at a macroscopic level, but the large number of particles makes these effects possible. For instance, both the Josephson effect and the hydrodynamic circulation in 4He depend on the existence of a macroscopic complex scalar wavefunction or order parameter. In fact, if the superconductor becomes too small, effects like the Josephson effect, flux quantization and persistent currents all start to get washed out. There is a gigantic energy barrier preventing the decay from the n=1 current-carrying state to the n=0 current non-carrying state due to the large number of particles involved (i.e. the higher winding number state is meta-stable). As one decreases the number of particles, the energy barrier is lowered and the system can start to tunnel from the higher winding number state to the lower winding number state.

In the quantum Hall effect, the samples need to be macroscopically large to prevent the boundaries from interacting with each other. Once the states on the edges are able to do that, they may hybridize and the conductance quantization gets washed out. This has been visualized in the context of 3D topological insulators using angle-resolved photoemission spectroscopy, in this well-known paper. Again, a large sample is needed to observe the effect.

It is interesting to think about where else such a robust quantization may arise in condensed matter physics. I suspect that there exist similar kinds of effects in different settings that have yet to be uncovered.

Aside: If you are skeptical about the multiply-connected nature of the quantum Hall effect, you can read about Laughlin’s gauge argument in his Nobel lecture here. His argument critically depends on a multiply-connected geometry.

On Science and Meaning

The history of science has provided strong evidence to suggest that the humanity’s place in the universe is not very special. We have not existed for very long in the history of the universe, we are not at the center of the universe and we likely will not exist in the future of the universe. This kind of sentiment can seem depressing to some, as can be seen in the response to the video made by Neil DeGrasse Tyson and MinutePhysics:

It appears that such ideas can make human life and our actions here on earth (and beyond) seem rather meaningless. As I have referenced in a previous post, this can especially be true for graduate students! However, on a more serious note, I would contend the exact opposite.

Because life on earth is so fragile and transient and only exists in some far-flung corner on the universe, the best thing we can hope to do as humans is celebrate our existence through acts of exploration, beauty, creation, truth and acts that enrich the lives of others and our environment.

When working in the lab or on a calculation that requires attention to small details, this larger context is often forgotten. To my mind, it is important not to lose sight of the basic reason why we are there in the first place, which is all too easy to do. The universe can seem meaningless, but not so when she lets us peer into her depths, usually revealing order of spectacular beauty.

I apologize if this post comes off as a little preachy or pretentious– I suspect I am really the one that needed this pep talk.