Extended hydrodynamic approach to quantum-classical nonequilibrium evolution. II. Application to nonpolar solvation.

Area of Science:

• Chemical Physics
• Theoretical Chemistry
• Computational Chemistry

Background:

• Quantum-classical methods are essential for simulating chemical dynamics.
• Hydrodynamic representations offer a novel approach to the classical sector.
• Nonequilibrium solvation dynamics present significant computational challenges.

Purpose of the Study:

• To apply a mixed quantum-classical formulation to nonequilibrium nonpolar solvation dynamics.
• To investigate the solvation dynamics of electronically excited NO in a rare gas environment.
• To compare the performance of different closure schemes for hydrodynamic equations.

Main Methods:

• Utilized a mixed quantum-classical formulation based on a hydrodynamic representation.
• Derived explicit equations of motion for populations and coherences for multi-quantum states.
• Employed Gauss-Hermite closure, dynamical density functional theory, and generalized Maxwellian closure schemes.

Main Results:

• The mixed quantum-classical method successfully modeled nonequilibrium solvation dynamics.
• The choice of closure scheme significantly impacted the simulated dynamics.
• Suitability of closure schemes depended on initial conditions and the nonequilibrium nature of the system.

Conclusions:

• The developed mixed quantum-classical approach provides a valuable tool for studying solvation dynamics.
• Closure approximations must be carefully selected based on the specific system and dynamics.
• This work advances the understanding of quantum-classical dynamics in condensed phases.