A Linear Response GOSTSHYP/COSMO Framework for Excited States in High Pressure Environments

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Spectroscopy

Background:

• Understanding pressure effects on molecular excited states is crucial for various chemical and physical processes.
• Existing methods often struggle to accurately model these effects, especially in different solvent environments.

Purpose of the Study:

• To develop and implement a robust theoretical framework for investigating pressure-induced effects on excited states.
• To apply this method to aromatic hydrocarbons in various solvents and compare with experimental results.

Main Methods:

• Kohn-Sham density functional theory (KS-DFT) for electronic structure calculations.
• Combination of GOSTSHYP and COSMO models for environmental effects.
• Development and implementation of a consistent linear response approach within the Turbomole program suite.

Main Results:

• Accurate prediction of pressure-induced spectral shifts for aromatic hydrocarbons in both nonpolar and polar solvents.
• Successful modeling of anomalous effects, such as those observed in azulene.
• Demonstration of the formalism's applicability to various response properties.

Conclusions:

• The developed KS-DFT-based linear response approach provides a reliable tool for studying pressure effects on excited states.
• The method shows excellent agreement with experimental data, highlighting its potential for future theoretical investigations.