Path integral Liouville dynamics for thermal equilibrium systems

作者：Liu, Jian^*

来源：Journal of Chemical Physics, 2014, 140(22): 224107.

DOI：10.1063/1.4881518

• VIBRATIONAL-ENERGY RELAXATION
• BACKWARD SEMICLASSICAL DYNAMICS
• CENTROID MOLECULAR-DYNAMICS
• TIME-CORRELATION-FUNCTIONS
• QUANTUM-STATISTICAL MECHANICS
• LIQUID PARA-HYDROGEN
• RATE CONSTANTS
• ALGORITHMS
• SIMULATION
• APPROXIMATION

We show a new imaginary time path integral based method-path integral Liouville dynamics (PILD), which can be derived from the equilibrium Liouville dynamics [J. Liu and W. H. Miller, J. Chem. Phys. 134, 104101 (2011)] in the Wigner phase space. Numerical tests of PILD with the simple (white noise) Langevin thermostat have been made for two strongly anharmonic model problems. Since implementation of PILD does not request any specific form of the potential energy surface, the results suggest that PILD offers a potentially useful approach for general condensed phase molecular systems to have the two important properties: conserves the quantum canonical distribution and recovers exact thermal correlation functions (of even nonlinear operators, i.e., nonlinear functions of position or momentum operators) in the classical, high temperature, and harmonic limits.

• 出版日期2014-6-14
• 单位北京大学