Analytic Computation of Vibrational Circular Dichroism Spectra Using Second-Order Møller-Plesset Perturbation Theory

Fuente: arXiv
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Main Authors: Shumberger, Brendan M., Pearce, Kirk C., Crawford, T. Daniel
Format: Preprint
Published: 2025
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author Shumberger, Brendan M.
Pearce, Kirk C.
Crawford, T. Daniel
author_facet Shumberger, Brendan M.
Pearce, Kirk C.
Crawford, T. Daniel
contents 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.
format Preprint
id arxiv_https___arxiv_org_abs_2501_06632
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Analytic Computation of Vibrational Circular Dichroism Spectra Using Second-Order Møller-Plesset Perturbation Theory
Shumberger, Brendan M.
Pearce, Kirk C.
Crawford, T. Daniel
Chemical Physics
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.
title Analytic Computation of Vibrational Circular Dichroism Spectra Using Second-Order Møller-Plesset Perturbation Theory
topic Chemical Physics
url https://arxiv.org/abs/2501.06632