Premium
Effect of dimer formation via hydrogen bonding on static and dynamic nonlinear optical characteristics of chromophores
Author(s) -
Shalin Nikita I.,
Fominykh Olga D.,
Balakina Marina Yu.
Publication year - 2020
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26061
Subject(s) - hyperpolarizability , dimer , chemistry , chromophore , hydrogen bond , superposition principle , molecular physics , acceptor , basis set , computational chemistry , atomic physics , nonlinear optical , nonlinear system , density functional theory , photochemistry , molecule , physics , quantum mechanics , organic chemistry
The effect of head‐to‐tail azochromophore dimer formation on the values of static and dynamic first hyperpolarizability is studied on the basis of calculations performed at M06‐2X/aug‐cc‐pVDZ and ωB97X‐D/aug‐cc‐pVDZ computational levels; the results are compared with those obtained at second‐order Moller‐Plesset pertubation theory (MP2)/aug‐cc‐pVDZ. Azochromophores DO3 and AAB‐DCV , participating in the dimer formation, contain nitro‐ or dicyanovinylene acceptor moieties. The structure of the studied dimers is obtained at the B3LYP‐D3/6‐31++G (d,p) level with basis set superposition error (BSSE) correction. Dynamic first hyperpolarizabilities are calculated at radiation frequencies of 0.65 eV, 0.918 eV and 1.165 eV. The essential effect of dimer formation is demonstrated: it results in almost a 3.5 times increase of the first hyperpolarizability. In the series D1 ‐ D2 ‐ D3 , β(2ω) values at 0.65 eV increase in a way similar to the static case: β(2ω) for D2 and D3 are 1.5 and 1.8 times higher than that for D1 . The notable resonance enhancement of β(2ω) for the studied hydrogen‐bonded dimers is demonstrated at radiation frequency of 1.165 eV.