Beyond the Rosenfeld Equation: Computation of Vibrational Circular Dichroism Spectra for Anisotropic Solutions.

Abstract

The difference in absorption of left and right circularly polarized light by chiral molecules can be described by the Rosenfeld equation for isotropic samples. It allows the assignment of the absolute stereochemistry by comparing experimental and computationally derived spectra. Despite the simple form of the Rosenfeld equation, its evaluation in the infrared regime remained challenging, as the contribution from the magnetic dipole operator is zero within the Born-Oppenheimer (BO) approximation. In order to resolve this issue, "beyond BO" theories had to be developed, among which Stephen's magnetic field perturbation (MFP) approach offers a computationally easily accessible form. In this work, optical activity is discussed for cylindrically symmetric solutions, which cannot be described anymore by Rosenfeld's equation due to broken spherical symmetry. Mathematical properties of natural and electric-field induced anisotropies are discussed on the basis of the gauge-independent theoretical framework of Buckingham and Dunn. The issue of achiral noise arising from external field perturbations is considered, and potential remedies are introduced. Natural anisotropic vibrational circular dichroism (VCD) equations are solved numerically by applying the MFP approach within the Hartree-Fock (HF) formalism. Properties of anisotropic VCD spectra are discussed for R-(+)-methyloxirane and (1 S,2 S)-cyclopropane-1,2-dicarbonitrile. In particular, by using a group theoretical argument, a gauge-independent lower bound for the quadrupole contribution of C2-symmetric molecules can be identified, which allows the importance of additional quadrupole terms in anisotropic VCD spectra calculation to be assessed.