Long-range corrected density functional theory study on static second hyperpolarizabilities of singlet diradical systems

Ryohei Kishi, Sean Bonness, Kyohei Yoneda, Hideaki Takahashi, Masayoshi Nakano, Edith Botek, Benoit Champagne, Takashi Kubo, Kenji Kamada, Koji Ohta, Takao Tsuneda

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Within the spin-unrestricted density functional theory (DFT) the long-range correction (LC) scheme combined with the Becke-Lee-Yang-Parr exchange-correlation functional, referred to as LC-UBLYP method, has been applied to the calculation of the second hyperpolarizability (γ) of open-shell singlet diradical systems of increasing complexity and has demonstrated good performance: (i) for the simplest H2 dissociation model, the γ values calculated by the LC-UBLYP method significantly overshoot the full configuration interaction result but reproduce qualitatively the evolution of γ as a function of the diradical character, (ii) for small singlet diradical 1,3-dipole systems, the diradical character dependence of γ determined by the UCCSD and UCCSD(T) reference methods is reproduced semiquantitatively by the LC-UBLYP method except in the small diradical character region, where the spin-unrestricted solutions coincide with spin-restricted solutions, (iii) the LC-UBLYP method also closely reproduces the UCCSD(T) results on the diradical character dependence of γ of the p -quinodimethane model system, particularly in the intermediate and large diradical character regions, whereas it shows an abrupt change for a diradical character (y) close to 0.2 originating from the triplet instability, (iv) the reliability of LC-UBLYP to reproduce reference coupled cluster results on open-shell singlet systems with intermediate and large diradical characters has also been substantiated in the case of γ of 1,4-bis-(imidazol-2-ylidene)- cyclohexa-2,5-diene (BI2Y), then (v), for real systems built from a pair of phenalenyl radicals separated by a conjugated linker, the LC-UBLYP results have been found to closely match the UBHandHLYP values-which, for small systems are in good agreement with those obtained using correlated molecular orbital methods-whereas the UB3LYP results can be much different. These results are not only important from the viewpoint of an efficient determination of the nonlinear optical properties of open-shell singlet systems, but also from the viewpoint of defining new challenges for elaborating improved exchange-correlation functionals.

langue originaleAnglais
Numéro d'article094107
journalThe journal of chemical physics
Numéro de publication9
Les DOIs
Etat de la publicationPublié - 19 mars 2010

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