Solvated Nuclear–Electronic Orbital Structure and Dynamics

• Published in: Journal of chemical theory and computation Vol. 18; no. 3; pp. 1340 - 1346
• Main Authors: Wildman, Andrew, Tao, Zhen, Zhao, Luning, Hammes-Schiffer, Sharon, Li, Xiaosong
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 08.03.2022
• Subjects: Computational chemistry; Continuum modeling; Density functional theory; Dynamics; Electron transfer; Excitation; Protons; Quantum chemistry; Real time; Solvation; Time dependence
• ISSN: 1549-9618; 1549-9626; 1549-9626
• DOI: 10.1021/acs.jctc.1c01285

Nonadiabatic dynamical processes such as proton-coupled electron transfer and excited state intramolecular proton transfer have been the subject of much research. One of the promising theoretical methods to describe these processes is the nuclear–electronic orbital (NEO) approach. This approach inherently accounts for nuclear quantum effects within quantum chemistry calculations, and it has recently been extended to directly simulate nonadiabatic processes with the development of real-time NEO methods. These processes can also be significantly dependent on the surrounding chemical environment, however, and capturing the effects of the environment is often necessary for analyzing experimentally relevant systems. This work couples the NEO density functional theory and real-time time-dependent density functional theory approaches with solvation through the polarizable continuum model. The effects of this coupling are investigated for ground state properties, solvent-dependent vibrational frequencies, and direct excited state intramolecular proton transfer dynamics.