The dynamics of the electrons for a molecule in solution is coupled to the dynamics of its polarizable environment, i.e., the solvent. To theoretically investigate such electronic dynamics, we have recently developed equations of motion (EOM) for the apparent solvent polarization charges that generate the reaction field in the Polarizable Continuum Model (PCM) for solvation and we have coupled them to a real-time time-dependent density functional theory (RT TDDFT) description of the solute [S. Corni et al., J. Phys. Chem. A 119, 5405 (2014)]. Here we present an extension of the EOM-PCM approach to a Time-Dependent Configuration Interaction (TD CI) description of the solute dynamics, which is free from the qualitative artifacts of RT TDDFT in the adiabatic approximation. As tests of the developed approach, we investigate the solvent Debye relaxation after an electronic excitation of the solute obtained either by a π pulse of light or by assuming the idealized sudden promotion to the excited state. Moreover, we present EOM for the Onsager solvation model and we compare the results with PCM. The developed approach provides qualitatively correct real-time evolutions and is promising as a general tool to investigate the electron dynamics elicited by external electromagnetic fields for molecules in solution.

Equation of motion for the solvent polarization apparent charges in the polarizable continuum model: Application to time-dependent CI / Pipolo, Silvio; Corni, Stefano; Cammi, Roberto. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 146:6(2017), p. 064116. [10.1063/1.4975620]

Equation of motion for the solvent polarization apparent charges in the polarizable continuum model: Application to time-dependent CI

CAMMI, Roberto
2017

Abstract

The dynamics of the electrons for a molecule in solution is coupled to the dynamics of its polarizable environment, i.e., the solvent. To theoretically investigate such electronic dynamics, we have recently developed equations of motion (EOM) for the apparent solvent polarization charges that generate the reaction field in the Polarizable Continuum Model (PCM) for solvation and we have coupled them to a real-time time-dependent density functional theory (RT TDDFT) description of the solute [S. Corni et al., J. Phys. Chem. A 119, 5405 (2014)]. Here we present an extension of the EOM-PCM approach to a Time-Dependent Configuration Interaction (TD CI) description of the solute dynamics, which is free from the qualitative artifacts of RT TDDFT in the adiabatic approximation. As tests of the developed approach, we investigate the solvent Debye relaxation after an electronic excitation of the solute obtained either by a π pulse of light or by assuming the idealized sudden promotion to the excited state. Moreover, we present EOM for the Onsager solvation model and we compare the results with PCM. The developed approach provides qualitatively correct real-time evolutions and is promising as a general tool to investigate the electron dynamics elicited by external electromagnetic fields for molecules in solution.
Equation of motion for the solvent polarization apparent charges in the polarizable continuum model: Application to time-dependent CI / Pipolo, Silvio; Corni, Stefano; Cammi, Roberto. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 146:6(2017), p. 064116. [10.1063/1.4975620]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2823356
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