C2 in a Box: Determining Its Intrinsic Bond Strength for the X(1)Σg(+) Ground State

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 lo...

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Bibliographic Details
Published in:Chemistry : a European journal 2016-03, Vol.22 (12), p.4087-4099
Main Authors: Zou, Wenli, Cremer, Dieter
Format: Article
Language:English
Online Access:Get full text
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Summary: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.
ISSN:1521-3765
DOI:10.1002/chem.201503750