title: Structures, properties and nature of DMSO-XY (XY=ClF and BrF) complexes: redshift and blueshift of S=O stretch.
abstract: The DMSO-XY (XY=ClF and BrF) complexes have been investigated with quantum chemical calculations. In general, two minima complexes were found, one with an O···X halogen bond and the other one with a S···X halogen bond. The former is more stable than the latter. Additionally, one first order saddle point complex was also observed. The interaction energies in the S complexes suffer a prominent influence from the calculation methods. At the CCSD(T)/aug-cc-pVDZ level, the interaction energies are calculated to be -9.19 and -12.73 kcal/mol for the Cl and Br global minima, respectively. Both complexes have also been evidenced to be stable at room temperature. The SO stretch vibration exhibits a red shift at the global minimum but a blue shift at the local minimum, whereas the CSC and CH stretch vibrations move to high frequency in both cases. The energy decomposition analyses indicate that the electrostatic interaction plays a dominant role in stabilizing these halogen-bonded complexes.
authors.affiliation: The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, PR China. liqingzhong1990@sina.com
authors.forename: Qing-Zhong
authors.initials: QZ
authors.lastname: Li
authors.forename: Wen-Rui
authors.initials: WR
authors.lastname: Xu
authors.forename: Ran
authors.initials: R
authors.lastname: Li
authors.forename: Xiao-Feng
authors.initials: XF
authors.lastname: Liu
authors.forename: Wen-Zuo
authors.initials: WZ
authors.lastname: Li
authors.forename: Jian-Bo
authors.initials: JB
authors.lastname: Cheng
mesh_terms: D004121:Dimethyl Sulfoxide / Q000737:chemistry*; D006219:Halogens / Q000737:chemistry*; D006860:Hydrogen Bonding; D008027:Light; D055672:Static Electricity; D013816:Thermodynamics; D014732:Vibration
chemical_list: D006219:Halogens; D004121:Dimethyl Sulfoxide