Linear response properties of solvated systems: a computational study.

Area of Science:

• Computational Chemistry
• Theoretical Chemistry
• Physical Chemistry

Background:

• Accurately calculating molecular polarizabilities in solution is crucial for understanding chemical and physical properties.
• Solvent effects significantly influence molecular electronic properties, necessitating sophisticated theoretical treatments.

Purpose of the Study:

• To computationally investigate static and dynamic linear polarizabilities of organic molecules in solution.
• To evaluate and compare different theoretical approaches for describing solvent effects on polarizability.

Main Methods:

• Utilized quantum mechanics/molecular mechanics (QM/MM) with non-polarizable and polarizable (fluctuating charge - FQ) force fields.
• Employed a multilevel Hartree-Fock (MLHF) quantum embedding method combined with the FQ model.
• Applied equation-of-motion coupled cluster (EOM-CC) response theory using multiscale approaches as reference wave functions.

Main Results:

• Calculated linear response properties for para-nitroaniline and benzonitrile in 1,4-dioxane, acetonitrile, and tetrahydrofuran.
• Analyzed computed polarizabilities based on electrostatic, polarization, and Pauli repulsion interactions.
• Compared computational results with available experimental data.

Conclusions:

• The study demonstrates the capability of various multiscale computational methods to accurately predict linear polarizabilities in solution.
• Different theoretical approaches provide distinct insights into the nature of solute-solvent interactions.
• The findings validate the use of these computational models for studying electronic properties of molecules in condensed phases.