title: C2 in a Box: Determining Its Intrinsic Bond Strength for the X(1)Σg(+) Ground State.
abstract: The intrinsic bond strength of C2 in its (1)Σg(+) ground state is determined from its stretching force constant utilizing MR-CISD+Q(8,8), MR-AQCC(8,8), and single-determinant coupled cluster calculations with triple and quadruple excitations. By referencing the CC stretching force constant to its local counterparts of ethane, ethylene, and acetylene, an intrinsic bond strength half way between that of a double bond and a triple bond is obtained. Diabatic MR-CISD+Q results do not change this. Confinement of C2 and suitable reference molecules in a noble gas cage leads to compression, polarization, and charge transfer effects, which are quantified by the local CC stretching force constants and differences of correlated electron densities. These results are in line with two π bonds and a partial σ bond. Bond orders and bond dissociation energies of small hydrocarbons do not support quadruple bonding in C2.
authors.affiliation: Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University, 3215 Daniel Ave, Dallas, Texas, 75275-0314, USA.
authors.forename: Wenli
authors.initials: W
authors.lastname: Zou
authors.affiliation: Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University, 3215 Daniel Ave, Dallas, Texas, 75275-0314, USA. dcremer@smu.edu.
authors.forename: Dieter
authors.initials: D
authors.lastname: Cremer
keywords: ab initio calculations; bond strength; carbon; force constants; quadruple bonds; space confinement analysis