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How are the charge transfer descriptors affected by the quality of the underpinning electronic density?
Author(s) -
Maschietto Federica,
Campetella Marco,
Frisch Michael J.,
Scalmani Giovanni,
Adamo Carlo,
Ciofini Ilaria
Publication year - 2018
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25144
Subject(s) - excited state , charge (physics) , statistical physics , density functional theory , character (mathematics) , transfer (computing) , quality (philosophy) , physics , chemistry , quantum mechanics , mathematics , computer science , geometry , parallel computing
With the aim of investigating qualitatively and quantitatively the impact of using excited state relaxed or unrelaxed density for the estimation of nature and characteristic of electronic excited states, we analyzed the behavior of 52 exchange correlation functionals for the prediction of density‐based indexes such as those recently introduced in literature to evaluate the charge transfer distance (D CT ) (Le Bahers et al. J. Chem. Theory Comput. 2011, 7, 2498) in the case of a prototype family of push–pull dyes. Our results show that while a qualitatively consistent assessment of the nature of the excited states is obtained using either the unrelaxed or the relaxed density, from a quantitative standpoint we observe large discrepancies in the charge transfer distance for electronic transitions having substantial CT character. This behavior is independent of nature of the exchange–correlation functional used. © 2018 Wiley Periodicals, Inc.