Ab-initio path integral techniques for molecules

Shin, Daejin; Ho, Ming-Chak; Shumway, J.

Ab-initio path integral techniques for molecules

Authors

Shin, Daejin

Ho, Ming-Chak

Shumway, J.

Description

Path integral Monte Carlo with Green's function analysis allows the sampling of quantum mechanical properties of molecules at finite temperature. While a high-precision computation of the energy of the Born-Oppenheimer surface from path integral Monte Carlo is quite costly, we can extract many properties without explicitly calculating the electronic energies. We demonstrate how physically relevant quantities, such as bond-length, vibrational spectra, and polarizabilities of molecules may be sampled directly from the path integral simulation using Matsubura (temperature) Green's functions (imaginary-time correlation functions). These calculations on the hydrogen molecule are a proof-of-concept, designed to motivate new work on fixed-node path-integral calculations for molecules.
9 pages, 6 figures