Can Semilocal Approximations to the Embedding Potential Tackle Charge-Transfer-to-Solvent Excitations? An Aqueous Thiocyanate Example

Article Article scientifique Article Can Semilocal Approximations to the Embedding Potential Tackle Charge-Transfer-to-Solvent Excitations? An Aqueous Thiocyanate Example eng 2025-10-06 2025-10-28 author Roy Pierre-Olivier Départment de Chimie Physique, Université de Genève, Quai Ernest-Ansermet 30, CH-1211 Genève 4, Switzerland. 428328 Chimie physique (groupe 5) (CHIF5) author Fu Mingxue 0009-0007-3284-3124 Départment de Chimie Physique, Université de Genève, Quai Ernest-Ansermet 30, CH-1211 Genève 4, Switzerland. 911914 author Sarangi Ronit Department of Chemistry, Syracuse University, Syracuse, New York 13244, United States.,Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482, United States. author Krylov Anna I 0000-0001-6788-5016 Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482, United States. author Wesolowski Tomasz Adam 0000-0001-5792-4616 Départment de Chimie Physique, Université de Genève, Quai Ernest-Ansermet 30, CH-1211 Genève 4, Switzerland. 92358 Département de chimie physique (CHIFI) 10452-10465 10.1021/acs.jctc.5c00991 41051255 1549-9618 PMC12573756 https://pubs.acs.org/doi/10.1021/acs.jctc.5c00991 Frozen-density embedding theory (FDET) provides a formal basis for methods employing density-dependent embedding potentials. FDET-based methods involve approximations concerning: (i) the choice of the approximant for the bifunctional v xct nad [ρA ,ρB ], (ii) the localization of the embedded wave function, and (iii) the approach used to generate the electron density of the environment. The set of approximations that has been shown to yield highly accurate complexation-induced shifts in vertical excitation energies for valence excitations localized on the chromophore─referred to as the "standard FDET protocol"─is expected to fail if applied to charge-transfer-to-solvent excitations. This work illustrates that such excitations can also be treated using an FDET-based method; however, they require refinement of the approximations used in the standard protocol. Dewey 540 38 Département de chimie physique 142 false 689 Groupe Wesolowski Journal of chemical theory and computation 21 20 1417319f-2271-4a67-bfb9-20cb1e4d22f2 Article (Published version) Public can-semilocal-approximations-to-the.pdf 6543760 application/pdf CC BY-4.0 f359d2d1c3bbacfb9a526c50865575021f689688c1751d0b23505aa4f7b44eb7 openAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie physique

Title	Published in	Access level	OA Policy	Year	Views	Downloads

Can Semilocal Approximations to the Embedding Potential Tackle Charge-Transfer-to-Solvent Excitations? An Aqueous Thiocyanate Example	Journal of chemical theory and computation			2025	8	49

Archive ouverte UNIGE

Roy, Pierre-Olivier

account_balance Affiliation entities

Affiliation entities