Wednesday, September 28, 2016

Deconstructing noise in organic charge transfer salts

There are several things that I used to find very puzzling about electrical noise measurements on the metallic phase of organic charge transfer salts.

The  measured noise spectrum is close to (but not exactly) 1/f.

The disparity of time/energy scales.
What is the relationship (if any) between the noise (which is sometimes measured on time scales as long as one thousand seconds (mHz)) and microscopics (which one might calculate with quantum chemistry and/or Hubbard models, but typically involves energies larger than meV or frequencies that can be ten orders of magnitude larger)?

Obscure trends.
If one looks at the actual exponent alpha of the noise, 1/f^alpha. It varies in a non-monotonic way as the temperature T varies. This looks rather "random" to me (i.e. I found it hard to believe there was any systematics involved).

However, Jens Muller and collaborators have used a model due to Dutta, Dimon, and Horn (DDH) to nicely elucidate what is going on in a series of papers such as this one.

Origin of the glass-like dynamics in molecular metals κ-(BEDT-TTF)2X: implications from fluctuation spectroscopy and ab initio calculations 
Jens Müller, Benedikt Hartmann, Robert Rommel, Jens Brandenburg, Stephen M Winter, and John A Schlueter

Here are the basic ideas of the DDH model.
There is a distribution of relaxation times tau, which arise because there are a distribution of activation energies E for relaxation.

tau0 is a typical "attempt frequency"/molecular vibration frequency for something like a conformational change of a molecule.
One assumes that for a specific tau that the noise is simply Lorentzian. But one then averages over D(E), the distribution of activation energies.

One can then show that at a given temperature the noise has a 1/f^alpha form with an exponent given by,
A specific consistency test of the model is to then compare the measured alpha to that calculated from the above expression using the observed temperature dependence of the noise spectrum. This comparison is shown in the figure above. 

One can also invert the equation above to extract D(E), giving the result in the figure below.

These two points give a better understanding of where the temperature dependence of alpha comes from; it has a reasonable explanation in terms of the distribution of activation energies.

Furthermore, the origin of the low frequency noise is the relatively large value of the activation energies. This leads to conformational transitions being extremely rare. In particular, I find it amazing that the noise at the Hz scale is detecting the fact that in the macroscopic crystal about every one second a single molecule (yes, just one undergoes a conformational change)!

Note that the activation energy distribution D(E) is peaked around 230 meV. This is the same energy that is deduced from studies of the activation energy for the glassy behaviour seen in NMR, specific heat, and thermal expansion. Moreover it is also the energy barrier calculated from quantum chemistry for the transition between the two conformations of the ethylene end groups (staggered vs. eclipsed) that I discussed in a recent post.

The reference given above also gives an explanation using ab initio calculations as to why the presence of the glass transition depends on the chemical identity of the anion X in kappa-(BEDT-TTF)2X. It relates to the relative strength of the bonding between X and the ethylene end groups of the BEDT-TTF molecules.

One thing that is not clear is what determines the width of the distribution D(E).

There are subtleties that I have glossed over here and other interesting things but the aim of this post is to focus on the big picture and some of my basic puzzles.

I thank Jens Muller for a very helpful discussion about his work.

Tuesday, September 27, 2016

Tutorial on bad metals

After yesterday's colloquium a large group of IISER students (both undergraduate and graduate) expressed an interest in having a tutorial on more of the subject of emergent quantum matter.
It is today at 6pm after they are done with the days lectures. This tells you something about the quality of the students and institution!

I am going to give a tutorial about bad metals. I will probably cover half of these slides. Hopefully there will be lots of questions and side discussions on the blackboard.

Wednesday, September 21, 2016

A minor detail that matters in organic charge transfer salts

One helpful way to think about condensed matter is in terms of relative energy scales. This can help one decide what is important and what is not.
However, this does not always work, particularly in complex systems where new low energy scales can emerge.

For a long time there has been a "minor detail" about organic charge transfer salts based on the BEDT-TTF molecule that I have found rather annoying and puzzling.
It concerns the role of ethylene end groups on the molecule and their possible different conformations (eclipsed vs. staggered).

Why should the conformations matter?

I would think not. The overlap of the relevant electronic molecular orbitals which are largely centred on sulphur atoms are negligible as seen below in the HOMO (Highest Occupied Molecular Orbital) for a BEDT-TTF dimer.

The figures are taken from this paper by Edan Scriven and Ben Powell.

However, things are more subtle than I would have thought.

Here are some of the significant effects that result from these two different conformations. They have different energies and by thermal annealing in a crystal you can convert between them.
As a result disorder in a crystal can be controlled by varying the cooling rate.
In some materials there is even a glass transition around 80 Kelvin.

Examples of the dramatic effects of the disorder can be seen.

Resistance vs. temperature curve (see for example the figure below taken from here).

Suppression of the superconducting transition temperature.
This can be seen in the curves above.

Electrical noise experiments

Another dramatic effect of the ethylene groups that is much larger than most people expect is
Isotopic substitution of the hydrogen with deuterium in the ethylene groups can drive the Mott metal-insulator transition. 
This somehow arises from a geometrical isotope effect associated with hydrogen bonds between the ethylene groups and the anion.

It turns out that changing the conformation of the end group can have a significant effect on the parameters in the Hubbard model, that is the simplest possible effective Hamiltonian for these materials.
This is shown in this recent paper which estimates these parameters using DFT-based electronic structure calculations and Wannier orbitals to map onto a tight-binding model.

Influence of molecular conformations on the electronic structure of organic charge transfer salts Daniel Guterding, Roser Valentí, and Harald O. Jeschke .

In particular in going from Eclipsed (E) to Staggered (S) or visa versa is enough to cross the Mott insulator-metal phase boundary.
This provides a framework to understand the experimental puzzles discussed above.

One minor quibble. 
The authors estimate the Hubbard paper U (Coulomb interaction) for two holes on a BEDT-TTF dimer with a formula which is only valid in a particular limit.
The general formula for the energy of  two electrons on a two site Hubbard model is
where Um is the Hubbard interaction on a single dimer, V is the inter site Coulomb repulsion and t is the intersite hopping. The authors are assuming that Um - Vm is much larger than 4t which Scriven and Powell argue is not the case.
This will lead to quantitative changes but not change the main point that the conformational changes can produce a significant change in the Hubbard model parameters; particularly a large enough change to cross the Mott insulator-metal phase boundary.

Later I will write about the noise measurements (which I puzzled about before) which turn out to be a very sensitive probe of these two molecular conformations and their interconversion.

I thank Jens Muller for very helpful discussions about this work.

Monday, September 19, 2016

SciPost is a great initiative towards restoring science to journals

"SciPost is a a complete scientific publication portal managed by active professional scientists."

It is worth checking out.
SciPost addresses many concerns I have about the current sorry state of science and publishing. These include that journals becoming redundant and counter productive and so we need alternative publication models, particularly not involving for-profit companies.

One thing I particularly like is the transparency. All the referee reports are public and referees have the option of being anonymous or not. Furthermore, anyone can write a report. Authors responses to the reports are also public.
I think this public accountability may raise standards significantly.

I hope you (and I) will consider supporting it by
-  submitting articles
- writing referee reports (either on request or volunteering)
- writing commentaries
- being willing to serve on the Editorial College

Jean-Sebastien Caux is to be commended for all the work he has put into this.
I thank Matt Davis for bringing this significant initiative to my attention.

Friday, September 16, 2016

A basic quantum concept: energy level repulsion (avoided crossings)

When I learnt and later taught basic quantum mechanics I don't think the notion of energy level repulsion (or equivalently avoided crossings) was emphasised (or even discussed?).

Much later I encountered the idea in advanced topics in theoretical physics such as random matrix theory and in theoretical chemistry  (non-adiabatic transitions and conical intersections).

Yet level repulsion is a very simple phenomena that can be illustrated with just a two by two matrix describing two coupled quantum states, as nicely discussed on the Wikipedia page.

Last semester when I was teaching Solid State Physics I realised just how central and basic the phenomena is and that the students did not appreciate this.

Level repulsion is the origin of several key phenomena in chemistry and physics.

In solid state physics, it is the origin of the appearance of band gaps at the zone boundary and thus the all important distinction between metals and insulators.

Previously, I posted how Chemistry is quantum science because chemical bonding (the lowering of energy due to interacting atoms) arises due to the superposition principle. This could also be viewed as level repulsion.

Another key idea in chemistry is that of transition states and activation energies for chemical reactions. When one uses a diabatic state picture, particularly as emphasised by Shaik and Warshel, the transition state emerges naturally in terms of level repulsion.

The figure is taken from here.

Can you think of any other nice examples?

Wednesday, September 14, 2016

Relating the Hall coefficient to thermodynamic quantities

Previously, I have posted about how in certain contexts one can relate non-equilibrium transport quantities to equilibrium thermodynamic quantities. This is particularly nice because for theorists it is usually a lot easier to calculate the latter than the former.
But, it should be stressed that all of these results are an approximation or only hold in certain limits.

Here are some examples.

The thermoelectric power can be related to the temperature derivative of the chemical potential through the Kelvin formula (illuminated by Peterson and Shastry).

A paper argues that the Weidemann-Franz ratio in a non-Fermi liquid can be related to the ratio of two different susceptibilities.

Work of Shastry showing that the high frequency limit of the Hall coefficient, Lorenz ratio and thermopower can be related to equilibrium correlation functions.

It has been suggested that the transverse thermoelectric conductivity (Nernst signal) due to superconducting fluctuations is closely related to the magnetisation.

Haerter, Pederson, and Shastry conjectured that for a doped Mott insulator on a triangular lattice that the Hall coefficient can be related to the temperature dependence of diamagnetic susceptibility.

Here I want to discuss some interesting results for the Hall coefficient R_H.
First,  remember that in a simple Fermi liquid (or a classical Drude model) with only one species of charge carrier of charge q and density n that

R_H=1/q n

Clearly this is a case where a rather complex transport quantity (which is actually a correlation function involving three currents) reduces to a simple thermodynamic quantity.

But, what about in strongly correlated systems?

There is a rarely cited paper from 1993

Sign of equilibrium Hall conductivity in strongly correlated systems 
 A. G. Rojo, Gabriel Kotliar, and G. S. Canright

It gives an argument of just a few lines that relates the Hall coefficient to the orbital magnetic susceptibility (Landau diamagnetism)

BTW. I think there is a typo in the very last equation. It should also contain a factor of the charge compressibility.

I am a bit puzzled by the derivation, because it appears to be completely rigorous and general. The derivation of the Kelvin formula for thermopower, also has this deceptive general validity. It turns out that "devil in the details" turns out to be that the two limits of sending frequency and wave vector to zero do not commute.

A related paper shows that with a certain limiting procedure the Hall response (at zero temperature) is related to the derivative of the Drude weight with respect to the density.

Reactive Hall Response
X. Zotos, F. Naef, M. Long, and P. Prelovšek

This is valuable because it gives a simple explanation of why in a doped Mott insulator the Hall coefficient can change sign as the doping changes.