Bonding in SCln (n=1-6): A Quantum Chemical Study

作者：Leiding Jeff^*; Woon David E; Dunning Thom H Jr

来源：Journal of Physical Chemistry A, 2011, 115(18): 4757-4764.

DOI：10.1021/jp2004024

Following a previous study of bonding and isomerism in the SFn and singly chloro-substituted SFn-1Cl (n = 1-6) series, we describe bonding in the ground and low-lying excited states of the completely substituted series, SCln (n = 1-6). All structures were characterized at least at the RCCSD(T)/aug-cc-pV(Q+d)Z level of theory. Both differences and similarities were observed between SCln and our previous results on SFn-1Cl and SFn. Several minimum structures that exist in SFn and SFn-1Cl are absent in SCln. For example, the optimized structure of SCl2((3)A(2)) is a transition state in C-s symmetry, whereas the analogous states are minima in SFn and SFn-1Cl. Second, we found a continuation of a trend discovered in the SFn-1Cl series, where Cl substitution has a destabilizing effect that weakens bonds with respect to SFn. This effect is much stronger in the SCln series than it is in the SFn-1Cl series, which is why SCl2 is the most stable observed species in the family and why SCl4, SCl5, and SCl6 are unstable (SCln-2 + Cl-2 additions are endothermic for n = 4-6).

• 出版日期2011-5-12