Simulation of Ab Initio Optical Absorption Spectrum of β‑Carotene with Fully Resolved S 0 and S 2 Vibrational Normal Modes

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2022-01, Vol.126 (2), p.180-189
• Main Authors: Jakučionis, Mantas, Gaižiu̅nas, Ignas, Šulskus, Juozas, Abramavičius, Darius
• Format: Article
• Language: English
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters; beta Carotene; Computer Simulation; Quantum Theory; Solvents; Vibration
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.1c06115

The electronic absorption spectrum of β-carotene (β-Car) is studied using quantum chemistry and quantum dynamics simulations. Vibrational normal modes were computed in optimized geometries of the electronic ground state S 0 and the optically bright excited S 2 state using the time-dependent density functional theory. By expressing the S 2-state normal modes in terms of the ground-state modes, we find that no one-to-one correspondence between the ground- and excited-state vibrational modes exists. Using the ab initio results, we simulated the β-Car absorption spectrum with all 282 vibrational modes in a model solvent at 300 K using the time-dependent Dirac–Frenkel variational principle and are able to qualitatively reproduce the full absorption line shape. By comparing the 282-mode model with the prominent 2-mode model, widely used to interpret carotenoid experiments, we find that the full 282-mode model better describes the high-frequency progression of carotenoid absorption spectra; hence, vibrational modes become highly mixed during the S 0 → S 2 optical excitation. The obtained results suggest that electronic energy dissipation is mediated by numerous vibrational modes.