[中文文摘]用分子图形软件设计出 4 9种硫原子团簇Sn+ (n =3～ 13)的结构 ,使用B3LYP密度泛函进行几何构型优化和振动频率计算 ,根据分子的总能量得出最稳定的同分异构体 .在硫原子团簇正离子中 ,大部分原子为二配位成键 .带有一、三配位的原子结构的总能量较高 .部分最稳定硫原子团簇正离子的构型与最稳定的中性硫原子团簇的构型完全不同.[英文文摘]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 6231G3 level for all sulfur atoms were performed using Gaus2
sian 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 one2fold , two2
fold and three2fold modes for modeling were considered , according to the bonding characteristics of the sulfur atom. Fi2
nally a total of eleven structures for S3
+ , S4+ and S5+ ; ten isomers of S6
+ and S7+ ; fifteen isomers of S8
+ and S9+ and thirteen isomers of S10
+ , S11+ , S12+ and S13
+ are acquired , respectively. A large number of structural possibilities of
non2minimum structures were not covered. According to total energies , the most stable Sn
+ ( n = 3～13) isomers are pre2
dicted. The geometry , relative stability and structural rules of these cationic sulfur clusters were described. Some struc2
tures of neutral sulfur clusters with true minima transform upon ionization into non2minimum cationic structures and vice
versa. The results of a large amount of calculations show that the two2fold coordination is generally favored in sulfur
cationic clusters , though some sulfur atoms coordinated with the others in one2fold or three2fold mode are higher in total
energy. The most stable isomer of some cationic clusters shows a structure completely different from that of the corre2
sponding neutral cluster. In chain structures , the atoms at the two ends adopt the one2fold mode and the others are in
two2fold mode. Theoretical studies on sulfur cationic structures with a three2fold atom are rare. It is unlikely to have a
sulfur cationic cluster in cage structure , for the bondings of a three2fold atom are not strong enough. The calculation
results can serve as guiding factors for future theoretical studies on large sulfur clusters.国家自然科学基金资助项目 (2 95 73117); 优秀国家重点实验室研究基金 (20023001
