Nonequilibrium Solvent Polarization Effects in Real-Time Electronic Dynamics of Solute Molecules Subject to Time-Dependent Electric Fields: A New Feature of the Polarizable Continuum Model

• Published in: Journal of chemical theory and computation Vol. 15; no. 4; pp. 2306 - 2319
• Main Authors: Gil, Gabriel, Pipolo, Silvio, Delgado, Alain, Rozzi, Carlo Andrea, Corni, Stefano
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 09.04.2019
• Series: Journal of Chemical Theory and Computation
• Subjects: Absorption spectra; Chemical Sciences; Computational chemistry; Continuum modeling; Density functional theory; Electric fields; or physical chemistry; Quantum mechanics; Real time; Solvation; Solvents; Theoretical and; Time dependence
• ISSN: 1549-9618; 1549-9626; 1549-9626
• DOI: 10.1021/acs.jctc.9b00010

We develop an extension of the time-dependent equation-of-motion formulation of the polarizable continuum model (EOM-TDPCM) to introduce nonequilibrium cavity field effects in quantum mechanical calculations of solvated molecules subject to time-dependent electric fields. This method has been implemented in Octopus, a state-of-the-art code for real-space, real-time time-dependent density functional theory (RT-TDDFT) calculations. To show the potential of our methodology, we perform EOM-TDPCM/RT-TDDFT calculations of trans-azobenzene in water and in other model solvents with shorter relaxation times. Our results for the optical absorption spectrum of trans-azobenzene show (i) that cavity field effects have a clear impact in the overall spectral shape and (ii) that an accurate description of the solute shape (as the one provided within PCM) is key to correctly account for cavity field effects.