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Solvent Effects on Electronically Excited States Using the Conductor-Like Screening Model and the Second-Order
Bernd Lunkenheimer1, Andreas Köhn1
1Institut für Physikalische Chemie, Johannes Gutenberg-Universität , 55099 Mainz, Germany.
Journal of Chemical Theory and Computation
|November 21, 2015
Summary
The conductor-like screening model (COSMO) method, using algebraic-diagrammatic construction through second-order (ADC(2)), accurately models solvent effects on excited states by considering both solute charge distribution changes and excitonic coupling. This approach is crucial for understanding excitation energies and properties.
Area of Science:
- Computational Chemistry
- Quantum Chemistry
- Theoretical Chemistry
Background:
- Solvent effects significantly influence molecular excited states.
- Previous continuum solvation models often neglect key contributions to solvent effects.
- Understanding these effects is vital for accurate prediction of spectroscopic properties.
Purpose of the Study:
- To implement and validate the conductor-like screening model (COSMO) for excited states within the algebraic-diagrammatic construction through second-order (ADC(2)) method.
- To analyze and incorporate both electronic and nuclear reorganization contributions to solvent effects.
- To investigate the role of excitonic coupling between solute and solvent in determining excited state properties.
Main Methods:
- Utilizing the conductor-like screening model (COSMO) for solvation.
- Employing the algebraic-diagrammatic construction through second-order (ADC(2)) method for correlated excited states.
- Considering both equilibrium and nonequilibrium solvent reorganization.
- Accounting for the coupling of transition densities with solvent electronic response.
Main Results:
- The study demonstrates that both solute charge reorganization and excitonic coupling with the solvent are essential for accurate excited-state calculations.
- Significant influence of both effects on excitation energies and properties was observed for acrolein (π-π* and n-π* excitations).
- Linear response contributions were found indispensable for screening effects in the ethene dimer.
Conclusions:
- A comprehensive treatment of solvent effects, including reorganization and excitonic coupling, is necessary for accurate excited-state calculations.
- The implemented ADC(2)-COSMO approach provides a robust framework for studying complex systems.
- The findings are applicable to various molecular systems, including dyads and intramolecular charge-transfer states.
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