Solvated Nuclear-Electronic Orbital Structure and Dynamics.

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Theoretical Chemistry

Background:

• Nonadiabatic dynamical processes, such as proton-coupled electron transfer and excited state intramolecular proton transfer, are crucial in chemical reactions.
• The nuclear-electronic orbital (NEO) approach accounts for nuclear quantum effects in quantum chemistry.
• Simulating these processes requires considering the surrounding chemical environment, which is often challenging.

Purpose of the Study:

• To extend the real-time NEO method to include environmental effects through solvation models.
• To investigate the coupling of NEO density functional theory (NEO-DFT) and real-time time-dependent density functional theory (RT-TDDFT) with the polarizable continuum model (PCM).
• To analyze the impact of this coupling on ground state properties, vibrational frequencies, and excited state intramolecular proton transfer dynamics.

Main Methods:

• Coupling of NEO-DFT and RT-TDDFT with the polarizable continuum model (PCM).
• Real-time simulation of nonadiabatic dynamics.
• Investigation of solvent effects on quantum chemical calculations.

Main Results:

• The coupled approach successfully simulates nonadiabatic processes, including excited state intramolecular proton transfer.
• Solvent effects significantly influence ground state properties and vibrational frequencies.
• The method provides accurate dynamics for experimentally relevant systems.

Conclusions:

• The developed computational framework accurately captures the interplay between nonadiabatic dynamics and the chemical environment.
• This method offers a powerful tool for studying complex chemical processes influenced by solvation.
• The findings pave the way for more accurate theoretical predictions in physical chemistry and spectroscopy.