Seminar (theoretical): Thomas F. Miller, III, California Institute of Technology

Thomas F. Miller, III - speaker's webpage
Division of Chemistry and Chemical Engineering
California Institute of Technology
Host: Garnet Chan

Quantum Dynamics from Classical Trajectories: Direct simulation of charge transfer in enzymes and molecular catalysts

Condensed-phase charge-transfer reactions are a central feature of many biological and synthetic catalytic pathways. The development of accurate, scalable methods to simulate and understand these reactions is thus a central challenge for chemical theory. In the talk, we will describe recently developed path-integral methods for the direct simulation of condensed-phase electron transfer, proton transfer, and proton-coupled electron transfer (PCET) reactions [1-3]. Specific applications will include (i) characterization of the role of nanometer-scale protein fluctuations in facilitating enzyme-catalyzed hydrogen transfer [4] and (ii) comparison of concerted vs. sequential reaction pathways for PCET in mixed-valence iron bi-imidazoline systems.

[1] Miller TF, "Isomorphic classical molecular dynamics model for an excess electron in a supercritical fluid,” J. Chem. Phys., 129, 194502 (2008).
[2] Ananth N and Milller TF, "Exact quantum statistics for electronically nonadiabatic systems using continuous path variables," J. Chem. Phys., 133, 234103 (2010).
[3] Menzeleev AR, Ananth N, and Miller TF, "Direct simulation of electron transfer using ring polymer molecular dynamics: Comparison with semiclassical instanton theory and exact quantum methods," J. Chem. Phys., 135, 074106 (2011).
[4] Boekelheide N, Salomón-Ferrer R, and Miller TF, "Dynamics and dissipation in enzyme catalysis," Proc. Natl. Acad. USA, 108, 16159 (2011).