A primary focus of our research is the development of dynamics simulation methods that reveal the mechanistic details of quantum mechanical reactions that are central to biological and molecular catalysis. The nature of this effort is three-fold: firstly, we work from the foundation of quantum statistical mechanics and semiclassical dynamics to develop path-integral methods that expand the scope and reliability of condensed-phase quantum dynamics simulations [1-3]. Secondly, we develop quantum embedding methods to improve the description of molecular interactions in systems with subtle electronic properties [4,5]. And finally, we apply these methods to the mechanistic features of condensed-phase systems, including enzyme reactions and inorganic electron-transfer and proton-coupled electron transfer (PCET) processes. In the talk, we will describe these theoretical approaches and their application to chemical reactions. We will particularly focus on the recent development of path-integral methods for the description of general, non-adiabatic reactions [3] and the application of this approach to biological charge transfer. [1] Habershon S, Manolopoulos DE, Markland TE, and Miller TF, " Ring polymer molecular dynamics: Quantum effects in chemical dynamics from classical trajectories in an extended phase space,” Annu. Rev. Phys. Chem., 64, 387 (2013). [2] Kretchmer JS and Miller TF, "Direct simulation of proton-coupled electron transfer across multiple regimes," J. Chem. Phys., 138, 134109 (2013). [3] Menzeleev AR, Bell F, and Miller TF, "Kinetically constrained ring-polymer molecular dynamics for non-adiabatic chemical reactions," J. Chem. Phys., 140, 064103 (2014). [4] Manby FR, Stella M, Goodpaster JD, and Miller TF. “A simple, exact density-functional theory embedding scheme.” J. Chem. Theory Comput., 8, 2564 (2012). [5] Goodpaster JD, Barnes TA, Manby FR, and Miller TF. ‘Accurate and systematically improvable density functional theory embedding for correlated wavefunctions.’ J. Chem. Phys., 140, 18A507 (2014).

New approaches to simulating biological and molecular catalysts

249th National Meeting (2015)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.

New approaches to simulating biological and molecular catalysts<br />