Monday, July 20, 2015

Quantum nuclear effects in condensed phase chemistry

I am currently in Telluride for a meeting on Quantum effects in condensed phase systems. Two years ago I attended a similar meeting and in preparing it has been helpful to re-read several posts I wrote stimulated by that meeting.

In my first post, I listed possible quantum effects [zero-point motion, tunnelling, geometric phases, entanglement, ...] and pointed how generally one expects a condensed phase environment [protein, glass, solvent] for a molecular system will tend to reduce these quantum effects by decoherence.

I then asked two big questions.
Are there any instances where the environment can
A. enhance quantum effects?
B. lead to qualitatively new effects (e.g. associated with collective degrees of freedom) that are absent in the gas phase?

I clarified what I meant by a trivial vs. non-trivial enhancement of a quantum effect, from a physics point of view. An example of a "trivial" enhancement is where the environment changes the molecular geometry to enhance the effect. But I stressed that such an enhancement may be highly valuable from a chemistry or biochemistry point of view.

In a comment, Gautam Menon suggested that the Surface Enhanced Raman scattering was a nice example of a non-trivial enhancement. It is certainly spectacular, with enhancements as large as 10^11. However, I am not sure this is the type of quantum effect I am thinking of. The actual mechanism of the effect is still debated [see this paper] and I am not qualified to consider the relative merits of the alternative explanations, but it does look to me like it could be viewed as a semi-classical effect.

Tom Miller suggested to me that the solvation of single electrons and the associated polarons may be a suitable example of B.

I suggested that there were two important organising principles for describing and understanding quantum nuclear effects
1. Competing quantum effects
2. Rate processes can be dominated by rare quantum events.

I am looking forward to the meeting.

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