Theoretical Study on Diradical Characters and Nonlinear Optical Properties of 1,3-Diradical Compounds
作者： Ryohei Kishi , Yusuke Murata , Michika Saito , Keisuke Morita , Manabu Abe
DOI: 10.1021/JP508657S
关键词:
摘要: We investigate the relationships between diradical character (y) and nonlinear optical (NLO) properties of open-shell 1,3-diradical compounds using broken-symmetry density functional theory method. The 2,2-substituent effects on structure–property relationship are clarified for several 1,3-diphenylcyclopentane-1,3-diyl derivatives, which known as systems with weak or intermediate π-single-bonding characters. parent (1a: X = H) is found to be almost pure (y ∼ 1) owing highest occupied molecular orbital (HOMO) lowest unoccupied (LUMO). energy gap determined by balance through-space coupling through bond effect. On other hand, introduction electron-withdrawing substituents at C2 position cyclopentane-1,3-diyls (1b: OH, 1c: F) decrease y-value additional through-bond interactions. As a result, 1b 1c ...
acs.org
harvard.edu
sci-hub.se 参考文章(88)
Benoît Champagne, Bernard Kirtman, Theoretical approach to the design of organic molecular and polymeric nonlinear optical materials Handbook of Advanced Electronic and Photonic Materials and Devices. pp. 63- 126 ,(2001) , 10.1016/B978-012513745-4/50073-1
Andrzej J. Sadlej, Manthos G Papadopoulos, Jerzy Leszczynski, Non-linear optical properties of matter : from molecules to condensed phases Springer. ,(2006)
Substituent Effects in Radical Chemistry D. Reidel Pub. Co. , Distributed in the U.S.A. and Canada by Kluwer Academic Publishers. ,(1986) , 10.1007/978-94-009-4758-0
M. Klobukowski, Ramón Carbó, Self-consistent field : theory and applications Elsevier. ,(1990)
Hari Singh Nalwa, Handbook of advanced electronic and photonic materials and devices Academic Press. ,(2001)
David J. Williams, Paras N. Prasad, Introduction to Nonlinear Optical Effects in Molecules and Polymers ,(1991)
Martin Head-Gordon, Characterizing unpaired electrons from the one-particle density matrix Chemical Physics Letters. ,vol. 372, pp. 508- 511 ,(2003) , 10.1016/S0009-2614(03)00422-6
Manabu Abe, Waldemar Adam, Werner M. Nau, Photochemical Generation and Methanol Trapping of Localized 1,3 and 1,4 Singlet Diradicals Derived from a Spiroepoxy-Substituted Cyclopentane-1,3-diyl Journal of the American Chemical Society. ,vol. 120, pp. 11304- 11310 ,(1998) , 10.1021/JA9822761
Fumio Kita, Waldemar Adam, Paul Jordan, Werner M. Nau, Jakob Wirz, 1,3-Cyclopentanediyl Diradicals: Substituent and Temperature Dependence of Triplet−Singlet Intersystem Crossing Journal of the American Chemical Society. ,vol. 121, pp. 9265- 9275 ,(1999) , 10.1021/JA991362D
Masayoshi Nakano, Ryohei Kishi, Tomoshige Nitta, Takashi Kubo, Kazuhiro Nakasuji, Kenji Kamada, Koji Ohta, Benoît Champagne, Edith Botek, Kizashi Yamaguchi, Second Hyperpolarizability (γ) of Singlet Diradical System: Dependence of γ on the Diradical Character Journal of Physical Chemistry A. ,vol. 109, pp. 885- 891 ,(2005) , 10.1021/JP046322X