Quantum ergodicity and energy flow in molecules

David Leitner University of Nevada Reno

Under what conditions does a molecule thermalize under its own internal dynamics, and if it does how long does it take? I will discuss a theoretical framework, local random matrix theory, that establishes criteria for quantum ergodicity and energy flow in the vibrational state space of large molecules. I will also discuss some of the ways in which both limitations to and the rate of energy flow in the vibrational state space impact the kinetics of conformational isomerization in gas and condensed phase [1], reactions involving molecules attached to plasmonic nanoparticles [2], as well as thermal conductance of molecular junctions [3], which can now be measured for single molecules [4]. Comparison with results of a variety of experiments will be discussed.

[1.] Leitner, D. M. Quantum ergodicity and energy flow in molecules. Adv. Phys. 2015, 64, 445 - 517.

[2.] Poudel, H.; Shaon, P. H.; Leitner, D. M. Vibrational Energy Flow in Molecules Attached to Plasmonic Nanoparticles. J. Phys. Chem. C 2024, 128, 8628 - 8636.

[3.] Reid, K. M.; Pandey, H. D.; Leitner, D. M. Elastic and inelastic contributions to thermal transport between chemical groups and thermal rectification in molecules. J. Phys. Chem. C 2019, 6256 - 6264.

[4.] Cui, L.; Hur, S.; Zkbar, Z. A.; Klöckner, J. C.; Jeong, W.; Pauly, F.; Jang, S.-Y.; Reddy, P.; Meyhofer, E. Thermal conductance of single-molecule junctions. Nature 2019, 572, 628 - 633.