Electron donor solvent effects on the (hyper) polarizabilities of a solute presenting singlet diradical character

Hideaki Takahashi, Kazuki Kubota, Hitoshi Fukui, Sean Bonness, Kyohei Yoneda, Ryohei Kishi, Takashi Kubo, Kenji Kamada, Koji Ohta, Benoît Champagne, Edith Botek, Masayoshi Nakano

Research output: Chapter in Book/Report/Conference proceedingConference contribution

2 Citations (Scopus)

Abstract

We study the (hyper)polarizabilities of a singlet diradical molecule (2-borapropane-1,3-diyl) which contains a boron atom. For the purpose to control the (hyper)polarizabilities by tuning the diradical character of the boron compound, we employ water solvent as an electron donor to the boron atom. A series of quantum chemical calculations reveal that the electron donation from the lone pair of electrons in a water molecule to the vacant p orbital of boron atom gives rise to the increase of the diradical character, leading to the large variation of the polarizability of the molecule. We also investigate the solvation effects of the bulk water by utilizing the polarizable continuum model (PCM). It is shown that the PCM environment significantly increases the degree of enhancement of the second hyperpolarizability in the intermediate diradical regime of the compound. These results suggest that a singlet diradical boron compound immersed in an electron donor solvent can exhibit efficient third-order nonlinear optical properties, which can be tuned by designing the solute-solvent interactions. We examine the reliability of the PCM results by performing the additional QM/MM simulations. It is found that the QM/MM solvation effects slightly decrease the polarizability in contrast to the PCM calculation, which implies the possibility that PCM tends to overestimate the polarizability due to the lack of the ability to represent the solvation structures.

Original languageEnglish
Title of host publicationInternational Conference of Computational Methods in Sciences and Engineering 2009, ICCMSE 2009
Pages899-902
Number of pages4
DOIs
Publication statusPublished - 2012
Externally publishedYes
EventInternational Conference of Computational Methods in Sciences and Engineering 2009, ICCMSE 2009 - Rhodes, Greece
Duration: 2009 Sep 292009 Oct 4

Publication series

NameAIP Conference Proceedings
Volume1504
ISSN (Print)0094-243X
ISSN (Electronic)1551-7616

Other

OtherInternational Conference of Computational Methods in Sciences and Engineering 2009, ICCMSE 2009
CountryGreece
CityRhodes
Period09/9/2909/10/4

Keywords

  • (hyper) Polarizability
  • Diradical Character
  • Kohn-Sham DFT
  • NLO material
  • PCM
  • QM/MM

ASJC Scopus subject areas

  • Physics and Astronomy(all)

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