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D ∞h B 2 (BS) 2 −/2− and T d B(BS) 4 − : Boron sulfide clusters containing BB multiple bonds and B − tetrahedral centers
Author(s) -
Yao WenZhi,
Guo JinChang,
Lu HaiGang,
Li SiDian
Publication year - 2010
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22452
Subject(s) - crystallography , boron , chemistry , center (category theory) , singlet state , molecule , hydride , physics , atomic physics , stereochemistry , metal , excited state , organic chemistry
A density functional theory investigation on the geometrical and electronic properties of B 4 S 2 0/−/2−(B 2 (BS) 2 0/−/2− ) and B 5 S 4 0/−(B(BS) 4 0/− ) clusters has been performed in this work. Both the doublet B 2 (BS) 2 −([SBBBBS] − ) (D ∞h , 2 Π u ) and the singlet B 2 (BS) 2 2−([SBBBBS] 2− ) (D ∞h , 1 Σ g + ) proved to have perfect linear ground‐state structures containing a multiply bonded BB core (BB or BB) terminated with two BS groups, while T d B(BS) 4 −turned out to possess a perfect B − tetrahedral center directly corrected to four BS groups, similar to the corresponding boron hydride molecules of D ∞h B 2 H 2 − , D ∞h B 2 H 2 2− , and T d BH 4 − , respectively. B 4 S 2 and B 5 S 4 neutrals, however, appeared to be much different: they favor a planar fan‐shaped C 2v B 4 S 2 (a di‐S‐bridged B 4 rhombus) and a planar kite‐like C 2v B 5 S 4 (a di‐S‐bridged B 3 triangle bonded to two BS groups), respectively. One‐electron detachment energies and symmetrical stretching vibrational frequencies are calculated for D ∞h B 2 (BS) 2 −and T d B(BS) 4 −monoanions to facilitate their future characterizations. Neutral salts of B 2 (BS) 2 Li 2 with an elusive BB triple bond and B(BS) 4 Li containing a tetrahedral B − center are predicted possible to be targeted in experiments. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010