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	Structural stabilities of small cationic sulfur clusters
	Chen, MD ; Chen MD(陈明旦) ; Liu, MH ; Liu MH(刘明宏) ; Liu, JW ; Liu JW(刘建文) ; Jiao, YC ; Jiao YC(焦毓才) ; Zhang, QE ; Zhang QE(张乾二)
	2002
关键词	cationic sulfur clusters isomers S-n(+) B3LYP density functional
英文摘要	The cations of sulfur clusters exhibit intensities of significance on the mass spectra of sulfur clusters generated in direct laser vaporization. To our knowledge, theoretical investigations on cationic sulfur clusters are rare. Forty-nine isomers of sulfur clusters were acquired by means of the molecular model design, molecular mechanics and semi-empirical PM3 and the recently proposed and widely used B3LYP hybrid, non-local, DFT method with basis set 6-31G *. To look for stable configurations, full geometry optimizations at the 6-31G * level for all sulfur atoms were performed using Gaussian 98 program packages. The initial models were constructed by means of breaking bond( s), making bond( s), adding atom( s), deleting atom( s), rotating fragment( s), translating fragment s) and merging fragment( s). The one-fold, two-fold and three-fold modes for modeling were considered, according to the bonding characteristics of the sulfur atom. Finally a total of eleven structures for S-3(+) , S-4(+) and S-5(+) : ten isomers of S-6(+) and S-7(+) ; fifteen isomers of S-8(+) and S-9(+) and thirteen isomers of S-10(+), S-11(+), S-12(+) and S-13(+) are acquired, respectively. A large number of structural possibilities of non-minimum structures were not covered. According to total energies, the most stable S-n(+) ( n = 3 similar to 13) isomers are predicted. The geometry, relative stability and structural rules of these cationic sulfur clusters were described. Some structures of neutral sulfur clusters with true minima transform upon ionization into non-minimum cationic structures and vice versa. The results of a large amount of calculations show that the two-fold coordination is generally favored in sulfur cationic clusters, though some sulfur atoms coordinated with the others in one-fold or three-fold mode are higher in total energy. The most stable isomer of some cationic clusters shows a structure completely different from that of the corresponding neutral cluster. In chain structures, the atoms at the two ends adopt the one-fold mode and the others are in two-fold mode. Theoretical studies on sulfur cationic structures with a three-fold atom are rare. It is unlikely to have a sulfur cationic cluster in cage structure, for the bondings of a three-fold atom are not strong enough. The calculation results can serve as guiding factors for future theoretical studies on large sulfur clusters.
语种	中文
出版者	SCIENCE CHINA PRESS
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/12293]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Chen, MD,Chen MD,Liu, MH,et al. Structural stabilities of small cationic sulfur clusters[J],2002.
APA	Chen, MD.,陈明旦.,Liu, MH.,刘明宏.,Liu, JW.,...&张乾二.(2002).Structural stabilities of small cationic sulfur clusters..
MLA	Chen, MD,et al."Structural stabilities of small cationic sulfur clusters".(2002).

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