Raman Optical Activity Spectra from Density Functional Perturbation Theory and Density-Functional-Theory-Based Molecular Dynamics

Abstract

We describe the calculation of Raman optical activity (ROA) tensors from density functional perturbation theory, which has been implemented into the CP2K software package. Using the mixed Gaussian and plane waves method, ROA spectra are evaluated in the double-harmonic approximation. Moreover, an approach for the calculation of ROA spectra by means of density functional theory-based molecular dynamics is derived and used to obtain an ROA spectrum via time correlation functions, which paves the way for the calculation of ROA spectra taking into account anharmonicities and dynamic effects at ambient conditions.

Recent Trends in Chiroptical Spectroscopy: Theory and Applications of Vibrational Circular Dichroism and Raman Optical Activity

“…Interesting AIMD applications appeared for solute‐solvent chirality transfer or modeling VCD spectra of a flexible molecule, 2‐butanol . The AIMD technique can also be extended to Raman scattering and Raman optical activity simulations …”

“…[70] The AIMD technique can also be extended to Raman scattering and Raman optical activity simulations. [71,72]…”

A systematic benchmarking of computational vibrational spectroscopy with DFTB3: Normal mode analysis and fast Fourier transform dipole autocorrelation function

“…FT‐DAC method has already been proven as an effective tool to calculate the vibrational spectrum using ab initio methods based on density functional theory (DFT) . For instance, Thomas et al used the FT‐DAC with ab initio molecular dynamics (AIMD) simulations to calculate the IR and Raman spectra of small molecules .…”

Localized molecular orbitals for calculation and analysis of vibrational Raman optical activity

“…[37]. Computational advances based on first principles have included molecules-in-molecules fragment approaches [38], density fitting with massive parallel calculations [33], coupled cluster [39], and Cartesian transfer [40] techniques as well as analytic calculation of ROA intensities [30,41,42], mode-selective ("intensity-tracking") methods [24,43,44], ROA spectra from ab initio molecular dynamics [45], and extension to resonance with electronically excited states [34,[46][47][48].…”