Mathematical and Computational Methods in Quantum Chemistry

A novel quantum dynamics method for thermal correlation functions

Jian Liu

Peking University


There is currently considerable effort focused on developing ways for including quantum mechanical effects in condensed phase molecular dynamics simulations. No method was able to have the two important properties: conserves the quantum canonical distribution and recovers exact thermal correlation function (of even nonlinear operators, i.e., nonlinear functions of position or momentum operators) in the classical, high temperature, and harmonic limits. We show a novel imaginary time path integral based dynamics method-path integral Liouville dynamics (PILD), which can accomplish the task and is practical for real molecular systems. We will focus on applying the method to vibrational spectra of a few molecules. Its application to isotope effects in the spectrum will also be discussed.