Implementation of the CCSD-PCM linear response function for frequency dependent properties in solution: application...

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Theoretical Chemistry

Background:

• Accurate prediction of molecular properties in solution is crucial for understanding chemical phenomena.
• Existing methods often struggle to account for solvent effects on electronic properties.
• Frequency-dependent properties are particularly challenging to compute accurately in condensed phases.

Purpose of the Study:

• To implement and validate a frequency-dependent linear response (LR) function for coupled cluster singles and doubles (CCSD) with a polarizable continuum model (PCM) for calculations in solution.
• To assess the accuracy and computational cost of this new method for calculating static and dynamic polarizability and specific rotation.
• To investigate the importance of solvent electronic response for determining the absolute configuration of chiral molecules.

Main Methods:

• Implementation of the frequency-dependent linear response (LR) function within the coupled cluster singles and doubles (CCSD) framework.
• Integration of the polarizable continuum model (PCM) to simulate solvent effects.
• Calculation of static and dynamic polarizability for various test molecules.
• Computation of specific rotation for chiral compounds.

Main Results:

• The study presents the first implementation of frequency-dependent LR-CCSD with PCM for solution-phase property calculations.
• Model calculations demonstrate that a common approximation for the LR function with solvation models recovers over 70% of the full response at a comparable computational cost to gas-phase calculations.
• Calculations of specific rotation for three compounds revealed that solvent electronic response is essential for correctly assigning absolute configurations, where gas-phase methods failed.

Conclusions:

• The developed method provides an accurate and computationally feasible approach for calculating frequency-dependent molecular properties in solution.
• Accounting for the electronic response of the solvent is critical for accurate predictions of specific rotation and assigning absolute configurations of chiral molecules.
• This work advances the capability of computational chemistry to model complex chemical systems in condensed phases.