title: Bonding in SCln (n = 1-6): a quantum chemical study.
abstract: Following a previous study of bonding and isomerism in the SF(n) and singly chloro-substituted SF(n-1)Cl (n = 1-6) series, we describe bonding in the ground and low-lying excited states of the completely substituted series, SCl(n) (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 SCl(n) and our previous results on SF(n-1)Cl and SF(n). Several minimum structures that exist in SF(n) and SF(n-1)Cl are absent in SCl(n). For example, the optimized structure of SCl(2)((3)A(2)) is a transition state in C(s) symmetry, whereas the analogous states are minima in SF(n) and SF(n-1)Cl. Second, we found a continuation of a trend discovered in the SF(n-1)Cl series, where Cl substitution has a destabilizing effect that weakens bonds with respect to SF(n). This effect is much stronger in the SCl(n) series than it is in the SF(n-1)Cl series, which is why SCl(2) is the most stable observed species in the family and why SCl(4), SCl(5), and SCl(6) are unstable (SCl(n-2) + Cl(2) additions are endothermic for n = 4-6).
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, United States. leiding@illinois.edu
authors.forename: Jeff
authors.initials: J
authors.lastname: Leiding
authors.forename: David E
authors.initials: DE
authors.lastname: Woon
authors.forename: Thom H
authors.initials: TH
authors.lastname: Dunning
mesh_terms: D002712:Chlorides / Q000737:chemistry*; D011789:Quantum Theory; D013455:Sulfur / Q000737:chemistry*
chemical_list: D002712:Chlorides; D013455:Sulfur