Analytic Computation of Vibrational Circular Dichroism Spectra Using Second-Order M{\o}ller-Plesset Perturbation Theory

TL;DR

This paper introduces an analytic method for calculating vibrational circular dichroism spectra using second-order Møller-Plesset perturbation theory, offering improved efficiency and accuracy over previous numerical approaches.

Contribution

The authors develop the first analytic-derivative formulation of VCD spectra at the MP2 level, significantly reducing computational cost and enabling fully analytic spectrum calculations.

Findings

Close agreement with finite-difference results validates the new method.

The approach is computationally less expensive with O(N^6) scaling.

First fully analytic VCD spectrum for (S)-methyloxirane at MP2 level reported.

Abstract

We present the first analytic-derivative-based formulation of vibrational circular dichroism (VCD) atomic axial tensors for second-order Moller-Plesset (MP2) perturbation theory. We compare our implementation to our recently reported finite-difference approach and find close agreement, thus validating the new formulation. The new approach is dramatically less computationally expensive than the numerical-derivative method with an overall computational scaling of $O(N^6)$. In addition, we report the first fully analytic VCD spectrum for (S)-methyloxirane at the MP2 level of theory.