Work

Path integral molecular dynamics for exact quantum statistics of multi-electronic-state systems

Year: 2017

Type: article

Abstract: An exact approach to compute physical properties for general multi-electronic-state (MES) systems in thermal equilibrium is presented. The approach is extended from our recent progress on path integral molecular dynamics (PIMD), Liu et al. [J. Chem. Phys. 145, 024103 (2016)] and Zhang et al. [J. Chem. Phys. 147, 034109 (2017)], for quantum statistical mechanics when a single potential energy surface is involved. We first define an effective potential function that is numerically favorable for MES-PIMD and then derive corresponding estimators in MES-PIMD for evaluating various physical properties. Its application to several representative one-dimensional and multi-dimensional models demonstrates that MES-PIMD in principle offers a practical tool in either of the diabatic and adiabatic representations for studying exact quantum statistics of complex/large MES systems when the Born-Oppenheimer approximation, Condon approximation, and harmonic bath approximation are broken.

Source: The Journal of Chemical Physics

DOI: 10.1063/1.5005059

Authors: Xinzijian Liu, Jian Liu

Institutions: Peking University, Beijing National Laboratory for Molecular Sciences

Language: English

Topic: Quantum, superfluid, helium dynamics

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: green

Funders: National Natural Science Foundation of China, Ministry of Science and Technology of the People's Republic of China

Awards: G6151930034, G6346867535, G6880094956