title: Solvatochromic Shifts in UV-Vis Absorption Spectra: The Challenging Case of 4-Nitropyridine N-Oxide.
abstract: 4-Nitropyridine N-oxide is a well-known molecular probe for which the experimental UV/vis absorption spectrum has been measured in a large number of solvents. Previous measurements and their analyses suggest a dominant role of the solvent hydrogen-bond donation (HBD) capability in the solvatochromic shifts measured for the absorption spectra. Herein, we analyze these solvatochromic effects using a series of complementary approaches, including empirical solvent parameters, high-level calculation of the excited-state dipole and polarizability, several flavors of the polarizable continuum model, as well as dynamics using an effective fragment potential (EFP) description of the solvent molecules. First, applying a recently proposed set of solvent parameters, we show the importance of dispersion interactions for non-HBD solvents. This statement confronts advanced coupled-cluster and multireference calculations of dipole moments and polarizabilities of both the ground and excited states in gas phase. We further address the pros and cons of implicit solvent models combined to time-dependent density functional theory (TD-DFT) in describing the solvents effects for all (HBD and non-HBD) media, the simplest linear-response approach turning out to be the most adequate. Finally, we show that the explicit TD-DFT/EFP2 models work correctly for HBD molecules and allow for restoration of the main experimental trends.
authors.affiliation: CEISAM , UMR CNRS 6230, BP 92208, 2 Rue de la Houssinière, 44322 Nantes, Cedex 3, France.
authors.forename: Šimon
authors.initials: Š
authors.lastname: Budzák
authors.affiliation: CEISAM , UMR CNRS 6230, BP 92208, 2 Rue de la Houssinière, 44322 Nantes, Cedex 3, France.
authors.forename: Adéle D
authors.initials: AD
authors.lastname: Laurent
authors.affiliation: CEISAM , UMR CNRS 6230, BP 92208, 2 Rue de la Houssinière, 44322 Nantes, Cedex 3, France.
authors.forename: Christian
authors.initials: C
authors.lastname: Laurence
authors.affiliation: Department of Chemistry, Faculty of Natural Sciences, Matej Bel University , Tajovského 40, SK-97400 Banská Bystrica, Slovak Republic.
authors.forename: Miroslav
authors.initials: M
authors.lastname: Medved'
authors.affiliation: CEISAM , UMR CNRS 6230, BP 92208, 2 Rue de la Houssinière, 44322 Nantes, Cedex 3, France.|Institut Universitaire de France , 103 bd Saint-Michel, F-75005 Paris, Cedex 05, France.
authors.forename: Denis
authors.initials: D
authors.lastname: Jacquemin