Full Optical Rotation Tensor at CCSD Level in the Modified Velocity Gauge

28 December 2020, Version 2
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

This work presents the first simulations of the full optical rotation (OR) tensor at coupled cluster with single and double excitations (CCSD) level in the modified velocity gauge (MVG) formalism. The CCSD-MVG OR tensor is origin independent, and each tensor element can in principle be related directly to experimental measurements on oriented systems. We compare the CCSD results with those from two density functionals, B3LYP and CAM-B3LYP, on a test set of 22 chiral molecules. The results show that the functionals consistently overestimate the CCSD results for the individual tensor components and for the trace (which is related to the isotropic OR), by 10-20% with CAM-B3LYP and 20-30% with B3LYP. The data show that the contribution of the electric dipole-magnetic dipole polarizability tensor to the OR tensor is on average twice as large as that of the electric dipole-electric quadrupole polarizability tensor. The difficult case of (1S,4S)-(–)-norbornenone also reveals that the evaluation of the former polarizability tensor is more sensitive than the latter. We attribute the better agreement of CAM-B3LYP with CCSD to the ability of this functional to better reproduce electron delocalization compared with B3LYP, consistently with previous reports on isotropic OR. The CCSD-MVG approach allows the computation of reference data of the full OR tensor, which may be used to test more computationally efficient approximate methods that can be employed to study realistic models of optically active materials.

Keywords

Optical Rotation Tensor
Linear Response
Coupled Cluster Theory
Modified Velocity Gauge

Supplementary materials

Title
Description
Actions
Title
cc-mvg-si
Description
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.