Accelerated "on-the-fly" coupled-cluster path-integral molecular dynamics: Impact of nuclear quantum effects on an asymmetric proton

TL;DR

This paper introduces an accelerated coupled-cluster path-integral molecular dynamics method that efficiently captures nuclear quantum effects and electron correlation, demonstrated on a proton shared by water and formaldehyde.

Contribution

It combines quantum ring-polymer contraction with a second-generation Car-Parrinello-like dynamics to enable feasible correlated PIMD calculations at finite temperature.

Findings

Nuclear quantum effects broaden covalent bond-length distributions.

Proton transfer probability decreases when quantum effects are included.

Electron correlation and nuclear quantum effects can counteract each other in magnetic properties.

Abstract

We present an accelerated ``on-the-fly'' coupled-cluster path-integral molecular dynamics (PIMD) method for finite-temperature simulations in which electron correlation and nuclear quantum effects are treated simultaneously. The approach is based on our quantum ring-polymer contraction (qRPC) technique, in which the inexpensive Hartree-Fock potential is evaluated on the full ring-polymer, while the expensive coupled-cluster correction is evaluated on the centroid only. This qRPC decomposition is combined with a second-generation Car-Parrinello-like dynamics of the Hartree-Fock reference and a basis-consistent extrapolation of the coupled-cluster and de-excitation amplitudes. The combination of all three acceleration layers is essential for making correlated PIMD calculations feasible. We apply the method to a proton shared by water and formaldehyde. Relative to classical nuclei, nuclear quantum effects broaden covalent X--H bond-length distributions, reduce the bias of the shared proton toward formaldehyde, and shift the mean proton-transfer coordinate from 0.206 to 0.135A. The probability of finding the proton closer to formaldehyde decreases from 81.7$\%$ to 61.1$\%$. The corresponding nuclear magnetic shielding tensors show that electron correlation and nuclear quantum effects are of comparable magnitude and can act in opposite directions. These results demonstrate that predictive simulations of asymmetric hydrogen bonds require a simultaneous treatment of correlated electronic structure and nuclear quantum fluctuations.