Computation of Solid-State Vibrational Circular Dichroism in the Periodic Gauge

• Published in: The journal of physical chemistry letters 2021-08, Vol.12 (30), p.7213-7220
• Main Authors: Jähnigen, Sascha, Zehnacker, Anne, Vuilleumier, Rodolphe
• Format: Article
• Language: English
• Subjects: Chemical Sciences; or physical chemistry; Physical Insights into Materials and Molecular Properties; Theoretical and
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.1c01682

We introduce a new theoretical formalism to compute solid-state vibrational circular dichroism (VCD) spectra from molecular dynamics simulations. Having solved the origin-dependence problem of the periodic magnetic gauge, we present IR and VCD spectra of (1S,2S)-trans-1,2-cyclohexanediol obtained from first-principles molecular dynamics calculations and nuclear velocity perturbation theory, along with the experimental results. Because the structure model imposes periodic boundary conditions, the common origin of the rotational strength has hitherto been ill-defined and was approximated by means of averaging multiple origins. The new formalism reconnects the periodic model with the finite physical system and restores gauge freedom. It nevertheless fully accounts for nonlocal spatial couplings from the gauge transport term. We show that even for small simulation cells the rich nature of solid-state VCD spectra found in experiments can be reproduced to a very satisfactory level.