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

Area of Science:

• Computational Chemistry
• Spectroscopy
• Quantum Chemistry

Background:

• Raman optical activity (ROA) provides valuable information about molecular structure.
• Accurate theoretical prediction of ROA spectra is crucial for experimental interpretation.
• Existing methods often neglect dynamic and anharmonic effects.

Purpose of the Study:

• To implement and validate a method for calculating ROA tensors using density functional perturbation theory.
• To develop an approach for ROA spectra calculation using density functional theory-based molecular dynamics.
• To enable the computation of ROA spectra considering anharmonicities and dynamic effects.

Main Methods:

• Calculation of ROA tensors from density functional perturbation theory.
• Implementation within the CP2K software package.
• Evaluation of ROA spectra using the mixed Gaussian and plane waves method in the double-harmonic approximation.
• Derivation of an approach for ROA spectra calculation via density functional theory-based molecular dynamics and time correlation functions.

Main Results:

• Successful implementation of ROA tensor calculations within CP2K.
• Evaluation of ROA spectra in the double-harmonic approximation.
• Development of a novel method for ROA spectra calculation using molecular dynamics, incorporating time correlation functions.

Conclusions:

• The developed methods allow for the calculation of ROA spectra from first principles.
• The molecular dynamics approach paves the way for including anharmonicities and dynamic effects.
• This work advances the theoretical prediction of ROA spectra under ambient conditions.