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Title: Planar dicyclic B{sub 6}S{sub 6}, B{sub 6}S{sub 6}{sup −}, and B{sub 6}S{sub 6}{sup 2−} clusters: Boron sulfide analogues of naphthalene

Abstract

Inorganic analogues of hydrocarbons or polycyclic aromatic hydrocarbons (PAHs) are of current interest in chemistry. Based upon global structural searches and B3LYP and CCSD(T) calculations, we present herein the perfectly planar dicyclic boron sulfide clusters: D{sub 2h} B{sub 6}S{sub 6} (1, {sup 1}A{sub g}), D{sub 2h} B{sub 6}S{sub 6}{sup −} (2, {sup 2}B{sub 3u}), and D{sub 2h} B{sub 6}S{sub 6}{sup 2−} (3, {sup 1}A{sub g}). These are the global minima of the systems, being at least 0.73, 0.81, and 0.53 eV lower in energy, respectively, than their alternative isomers at the CCSD(T) level. The D{sub 2h} structures feature twin B{sub 3}S{sub 2} five-membered rings, which are fused together via a B{sub 2} unit and terminated by two BS groups. Bonding analyses show that the closed-shell B{sub 6}S{sub 6}{sup 2−} (3) cluster possesses 10 delocalized π electrons, closely analogous to the bonding pattern of the aromatic naphthalene C{sub 10}H{sub 8}. The B{sub 6}S{sub 6}{sup −} (2) and B{sub 6}S{sub 6} (1) species are readily obtained upon removal of one or two π electrons from B{sub 6}S{sub 6}{sup 2−} (3). The results build a new analogous relationship between boron sulfide clusters and their PAH counterparts. The B{sub 6}S{sub 6}{sup −} (2) monoanionmore » and B{sub 6}S{sub 6}{sup 2−} (3) dianion can be effectively stabilized in neutral LiB{sub 6}S{sub 6} and Li{sub 2}B{sub 6}S{sub 6} salts, respectively.« less

Authors:
 [1]; ; ; ;  [2];  [2];  [3]
  1. Department of Chemistry and Chemical Engineering, Binzhou University, Binzhou 256603, Shandong (China)
  2. Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, Shanxi (China)
  3. (China)
Publication Date:
OSTI Identifier:
22415454
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 1; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BORON SULFIDES; CHEMICAL BONDS; CHEMISTRY; ELECTRONS; ISOMERS; LITHIUM COMPOUNDS; MOLECULAR CLUSTERS; NAPHTHALENE; POLYCYCLIC AROMATIC HYDROCARBONS; SALTS

Citation Formats

Li, Da-Zhi, Bai, Hui, Ou, Ting, Chen, Qiang, Li, Si-Dian, E-mail: hj.zhai@sxu.edu.cn, E-mail: lisidian@sxu.edu.cn, Zhai, Hua-Jin, E-mail: hj.zhai@sxu.edu.cn, E-mail: lisidian@sxu.edu.cn, and State Key Laboratory of Quantum Optics and Quantum Optics Devices, Shanxi University, Taiyuan 030006, Shanxi. Planar dicyclic B{sub 6}S{sub 6}, B{sub 6}S{sub 6}{sup −}, and B{sub 6}S{sub 6}{sup 2−} clusters: Boron sulfide analogues of naphthalene. United States: N. p., 2015. Web. doi:10.1063/1.4904289.
Li, Da-Zhi, Bai, Hui, Ou, Ting, Chen, Qiang, Li, Si-Dian, E-mail: hj.zhai@sxu.edu.cn, E-mail: lisidian@sxu.edu.cn, Zhai, Hua-Jin, E-mail: hj.zhai@sxu.edu.cn, E-mail: lisidian@sxu.edu.cn, & State Key Laboratory of Quantum Optics and Quantum Optics Devices, Shanxi University, Taiyuan 030006, Shanxi. Planar dicyclic B{sub 6}S{sub 6}, B{sub 6}S{sub 6}{sup −}, and B{sub 6}S{sub 6}{sup 2−} clusters: Boron sulfide analogues of naphthalene. United States. doi:10.1063/1.4904289.
Li, Da-Zhi, Bai, Hui, Ou, Ting, Chen, Qiang, Li, Si-Dian, E-mail: hj.zhai@sxu.edu.cn, E-mail: lisidian@sxu.edu.cn, Zhai, Hua-Jin, E-mail: hj.zhai@sxu.edu.cn, E-mail: lisidian@sxu.edu.cn, and State Key Laboratory of Quantum Optics and Quantum Optics Devices, Shanxi University, Taiyuan 030006, Shanxi. Wed . "Planar dicyclic B{sub 6}S{sub 6}, B{sub 6}S{sub 6}{sup −}, and B{sub 6}S{sub 6}{sup 2−} clusters: Boron sulfide analogues of naphthalene". United States. doi:10.1063/1.4904289.
@article{osti_22415454,
title = {Planar dicyclic B{sub 6}S{sub 6}, B{sub 6}S{sub 6}{sup −}, and B{sub 6}S{sub 6}{sup 2−} clusters: Boron sulfide analogues of naphthalene},
author = {Li, Da-Zhi and Bai, Hui and Ou, Ting and Chen, Qiang and Li, Si-Dian, E-mail: hj.zhai@sxu.edu.cn, E-mail: lisidian@sxu.edu.cn and Zhai, Hua-Jin, E-mail: hj.zhai@sxu.edu.cn, E-mail: lisidian@sxu.edu.cn and State Key Laboratory of Quantum Optics and Quantum Optics Devices, Shanxi University, Taiyuan 030006, Shanxi},
abstractNote = {Inorganic analogues of hydrocarbons or polycyclic aromatic hydrocarbons (PAHs) are of current interest in chemistry. Based upon global structural searches and B3LYP and CCSD(T) calculations, we present herein the perfectly planar dicyclic boron sulfide clusters: D{sub 2h} B{sub 6}S{sub 6} (1, {sup 1}A{sub g}), D{sub 2h} B{sub 6}S{sub 6}{sup −} (2, {sup 2}B{sub 3u}), and D{sub 2h} B{sub 6}S{sub 6}{sup 2−} (3, {sup 1}A{sub g}). These are the global minima of the systems, being at least 0.73, 0.81, and 0.53 eV lower in energy, respectively, than their alternative isomers at the CCSD(T) level. The D{sub 2h} structures feature twin B{sub 3}S{sub 2} five-membered rings, which are fused together via a B{sub 2} unit and terminated by two BS groups. Bonding analyses show that the closed-shell B{sub 6}S{sub 6}{sup 2−} (3) cluster possesses 10 delocalized π electrons, closely analogous to the bonding pattern of the aromatic naphthalene C{sub 10}H{sub 8}. The B{sub 6}S{sub 6}{sup −} (2) and B{sub 6}S{sub 6} (1) species are readily obtained upon removal of one or two π electrons from B{sub 6}S{sub 6}{sup 2−} (3). The results build a new analogous relationship between boron sulfide clusters and their PAH counterparts. The B{sub 6}S{sub 6}{sup −} (2) monoanion and B{sub 6}S{sub 6}{sup 2−} (3) dianion can be effectively stabilized in neutral LiB{sub 6}S{sub 6} and Li{sub 2}B{sub 6}S{sub 6} salts, respectively.},
doi = {10.1063/1.4904289},
journal = {Journal of Chemical Physics},
number = 1,
volume = 142,
place = {United States},
year = {Wed Jan 07 00:00:00 EST 2015},
month = {Wed Jan 07 00:00:00 EST 2015}
}