Open-Shell Singlet Nature and σ-/π-Conjugation Effects on the Third-Order Nonlinear Optical Properties of Si Chains: Polysilane and Poly(disilene-1,2-diyl)

The Journal of Physical Chemistry. a
Hiroshi MatsuiMasayoshi Nakano

Abstract

We theoretically investigate the open-shell singlet nature and σ-/π-conjugation effects on the longitudinal second hyperpolarizabilities (γ) of one-dimensional chains involving silicon-silicon bonds, that is, polysilane and poly(disilene-1,2-diyl), by comparison with their carbon analogues, polyethylene and polyacetylene, respectively. It is found that poly(disilene-1,2-diyl) has less bond length alternation than polyacetylene and that σ-conjugation of polysilane is less effective on the enhancement of γ than π-conjugation of polyacetylene, whereas π-conjugation of poly(disilene-1,2-diyl) indicates a more than 20 times greater enhancement of the γ than that of polyacetylene, which is known to be a typical nonlinear optical molecule with large γ, for one-dimensional chains involving 3-5 double bonds. Further theoretical analyses of poly(disilene-1,2-diyl) reveal the σ- and π-electrons contribute negatively and positively to the γ, respectively. The latter contribution is significantly larger than the former and thus causes the remarkable enhancement of γ amplitudes due to the emerging open-shell singlet nature in the long π-conjugation length.

References

Aug 6, 1999·Journal of Molecular Graphics & Modelling·B M Bode, M S Gordon
Aug 17, 2001·Nature·S KawataK Takada
Jan 5, 2002·Chemical Reviews·Satoshi Kawata, Yoshimasa Kawata
Apr 2, 2004·Nature Materials·Marin Soljacić, J D Joannopoulos
Jul 15, 2006·The Journal of Physical Chemistry. a·Masayoshi NakanoKizashi Yamaguchi
Jun 28, 2007·Angewandte Chemie·Iulia Bejan, David Scheschkewitz
Aug 19, 2007·Journal of the American Chemical Society·Kei UchiyamaMitsuo Kira
Oct 30, 2007·Journal of the American Chemical Society·Aiko FukazawaKohei Tamao
Mar 1, 1980·Talanta·H Sakurai, T Ishimitsu
Feb 20, 2009·Journal of the American Chemical Society·Takeaki IwamotoMitsuo Kira
Jul 4, 2009·Chemistry : a European Journal·Annemarie SchäferJames Y Becker
Feb 25, 2010·Nature·Philip P Power
May 15, 2010·Chemical Communications : Chem Comm·Takahiro SatoNorihiro Tokitoh
Oct 15, 2010·Journal of the American Chemical Society·Megumi KobayashiKohei Tamao
Jan 10, 2012·Physical Chemistry Chemical Physics : PCCP·Wolfgang W Schoeller, Edgar Niecke
May 10, 2013·The Journal of Physical Chemistry. a·Marc de WergifosseMasayoshi Nakano
Jul 5, 2013·The Journal of Chemical Physics·Masayoshi Nakano, Benoît Champagne
Aug 8, 2015·Nature Communications·Hong Sheng QuahJagadese J Vittal

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Citations

Nov 18, 2016·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Hiroshi MatsuiMasayoshi Nakano
Aug 7, 2018·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Jun-Ya FujiyoshiMasayoshi Nakano
Mar 22, 2018·The Journal of Physical Chemistry. a·Hiroshi MatsuiMasayoshi Nakano

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