Electronically Excited States in Solution via a Smooth Dielectric Model Combined with Equation-of-Motion Coupled Cluster Theory - Publication - MOST Wiedzy

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Electronically Excited States in Solution via a Smooth Dielectric Model Combined with Equation-of-Motion Coupled Cluster Theory

Abstract

We present a method for computing excitation energies for molecules in solvent, based on the combination of a minimal parameter implicit solvent model and the equation-of-motion coupled-cluster singles and doubles method (EOM-CCSD). In this method, the solvent medium is represented by a smoothly varying dielectric function, constructed directly from the quantum mechanical electronic density using only two tunable parameters. The solvent-solute electrostatic interactions are computed by numerical solution of the nonhomogeneous Poisson equation and incorporated at the Hartree-Fock stage of the EOM-CCSD calculation by modification of the electrostatic potential. We demonstrate the method by computing excited state transition energies and solvent shifts for several small molecules in water. Results are presented for solvated H 2 O, formaldehyde, acetone and trans-acrolein, which have low-lying n → π* transitions and associated blue shifts in aqueous solution. Comparisons are made with experimental data and other theoretical approaches, including popular implicit solvation models and QM/MM methods. We find that our approach provides surprisingly good agreement with both experiment and the other models, despite its comparative simplicity. This approach only requires modification of the Fock operator and total energy expressions at the Hartree-Fock level—solvation effects enter into the EOM-CCSD calculation only through the Hartree-Fock orbitals. Our model provides a theoretically and computationally simple route for accurate simulations of excited state spectra of molecules in solution, paving the way for studies of larger and more complex molecules.

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Authors (6)

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Details

Category:
Articles
Type:
artykuł w czasopiśmie wyróżnionym w JCR
Published in:
Journal of Chemical Theory and Computation no. 13, pages 5572 - 5581,
ISSN: 1549-9618
Language:
English
Publication year:
2017
Bibliographic description:
Howard J., Womack J., Dziedzic J., Skylaris C., Pritchard B., Crawford T.: Electronically Excited States in Solution via a Smooth Dielectric Model Combined with Equation-of-Motion Coupled Cluster Theory// Journal of Chemical Theory and Computation. -Vol. 13, nr. 11 (2017), s.5572-5581
DOI:
Digital Object Identifier (open in new tab) 10.1021/acs.jctc.7b00833
Verified by:
Gdańsk University of Technology

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