Multiconfigurational SCF and short-range DFT combined with polarizable density embedding: Comparison of linear-response and state-specific solvatochromic shifts of acrolein and para-nitrophenolate in water

Willem Van Den Heuvel, Peter Reinholdt, Hans Jørgen Aa Jensen, Jacob Kongsted*

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Abstract

The polarizable density embedding model is combined with the multiconfigurational self-consistent field and MC-srDFT electronic structure methods to calculate solvatochromic shifts of the n-π∗ absorption of acrolein and the π-π∗ absorption of the para-nitrophenolate anion in aqueous solution. Differences between linear-response (LR) and state-specific (SS) solvent shifts are analyzed by assessing the contributions of different terms in the solvent potential. This comparison shows that the differences are not only due to the intrinsically different response of LR and SS excitation energies to the polarizability of the environment but also due to a different response to the static part of the environment potential. These observations show that even in nonpolarizable environments, LR and SS calculations based on SCF (orbital optimization) methods do not necessarily agree on the spectral shift. The difference can be as large as, or even dominate, the difference due to dynamical polarization.

OriginalsprogEngelsk
TidsskriftJournal of Chemical theory and Computation
Vol/bind18
Udgave nummer10
Sider (fra-til)6231-6239
ISSN1549-9618
DOI
StatusUdgivet - 11. okt. 2022

Bibliografisk note

Funding Information:
Computations/simulations for the work described herein were supported by the DeIC National HPC Centre, SDU. We acknowledge the Independent Research Fund Denmark for financial support (grant ID: DFF-7014-00050B) and the Novo Nordisk Foundation (grant ID: NNF19OC0058144) for financial support.

Publisher Copyright:
© 2022 American Chemical Society.

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