Interpolated Wave Functions for Nonadiabatic Simulations with the Fixed-Node Quantum Monte Carlo Method

Published in The Journal of Chemical Physics, 2016

Recommended citation: N. M. Tubman, Y. Yang, S. Hammes-Schiffer, and D. M. Ceperley, "Interpolated Wave Functions for Nonadiabatic Simulations with th e Fixed-Node Quantum Monte Carlo Method, " ACS Symp. Ser. 1234, Chap. 3, pp 47-61 (2016).

Simulating nonadiabatic effects with many-body wave function approaches is an open field with many challenges. Recent interest has been driven by new algorithmic developments and improved theoretical understanding of properties unique to electron-ion wave functions. Fixed-node diffusion Monte Caro is one technique that has shown promising results for simulating electron-ion systems. In particular, we focus on the CH molecule for which previous results suggested a relatively significant contribution to the energy from nonadiabatic effects. We propose a new wave function ansatz for diatomic systems which involves interpolating the determinant coefficients calculated from configuration interaction methods. The calculated nonadiabatic contribution to the energy in the CH molecule is reduced compared to our previous results, but still remains the largest among the molecules under consideration.

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