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Revisiting the relationship between the bond length alternation and the first hyperpolarizability with range‐separated hybrid functionals
Author(s) -
Jacquemin Denis,
Perpéte Eric A.,
Ciofini Ilaria,
Adamo Carlo
Publication year - 2007
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.20849
Subject(s) - hyperpolarizability , polarizability , alternation (linguistics) , computational chemistry , bond length , range (aeronautics) , chemical physics , chemistry , conjugated system , molecular physics , materials science , crystallography , organic chemistry , molecule , crystal structure , polymer , linguistics , philosophy , composite material
We monitor the influence of the bond length alternation (BLA) modification on the static electronic polarizability and first hyperpolarizability of two polymethineimine oligomers. Four theoretical approaches are compared: HF, PBE0, LC‐ωPBE, and MP2. For the dodecamer, both HF and PBE0 are unable to foresee even the qualitative evolution of the first hyperpolarizability when varying the BLA. On the contrary, LC‐ωPBE provides (non)linear optics properties in agreement with MP2 results, especially for the longer chains. This confirms the interest of range‐separated hybrids for the computation of the (hyper)polarizabilities of extended π‐conjugated compounds. © 2007 Wiley Periodicals, Inc. J Comput Chem 2008