期刊
JOURNAL OF MOLECULAR GRAPHICS & MODELLING
卷 55, 期 -, 页码 33-40出版社
ELSEVIER SCIENCE INC
DOI: 10.1016/j.jmgm.2014.10.015
关键词
Dimer; Radical and cation; The second hyperpolarizability; Interlayer charge-transfer; DFT
类别
资金
- Natural Science Foundation of China [21173035]
Hexathiophenalenylium (HTPLY) has gained increasing attention for its interesting and potentially useful optical properties as a result of the enhancement in spin delocalization and charge-transfer of phenalenyl radicals, occasioned by the attachment of successive three disulfide linkages. Herein, we performed density functional theory to calculate the binding interactions, electronic absorption spectra and the second hyperpolarizabilities of cation and radical dimers of HTPLY and its nitro derivatives. It is found that the equilibrium structures of their dimers at fully staggered position are most stable. Among these pi dimers, radical dimers exhibit stronger binding interactions with respect to cation dimers. In addition, obvious red shifts in electronic spectra of radical dimers are dependent on the large interlayer charge-transfers. More importantly, radical dimers (3)[4](dim) and (1)[5](dim), exhibit a significant increase in the second hyperpolarizabilities as compared to cation dimers, which is due to lower excitation energies and larger interlayer charge-transfers. We believe that the results presented in this article shall provide important evidence for the large interlayer charge-transfers in enhancing the NLO properties of the pi dimers. (C) 2014 Elsevier Inc. All rights reserved.
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