Theoretical study of the potential energy surface governing the stereochemistry in ClC sub 2 H sub 4 reactions

Journal Article · Thu Feb 22 04:00:00 EST 1990 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100367a013· OSTI ID:6664643

Engels, B; Peyerimhoff, S D ^[1]; Skell, P S ^[2]

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1. Universitaet Bonn (West Germany)
2. Pennsylvania State Univ., University Park (USA)

Large-scale multireference configuration interaction calculations in a double-{xi}-type AO basis including polarization functions are carried out for the potential surface of the ClC{sub 2}H{sub 4} system. The charge distribution for various extreme points of the surface is discussed. The absolute minimum is found for an asymmetric ClC{sub 2}H{sub 4} structure. The symmetrical bridged nuclear conformation is also found to be stable with respect to dissociation into Cl + C{sub 2}H{sub 4}. The activation energy for rotation about the C-C axis is calculated to be around 18 kJ/mol, which is comparable to that for the 1,2 migration (around 26 kJ mol). The stereochemistry is governed by the fact that addition of Cl to C{sub 2}H{sub 4} (or dissociation) is a two-step reaction proceeding through a symmetrical intermediate. The direct addition pathway possesses a small barrier of about 8 kJ/mol.

• OSTI ID: 6664643
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Journal Issue: 4 Vol. 94:4; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKENES
CALCULATION METHODS
CHLORINE
DATA
DATA ANALYSIS
ELEMENTS
ENERGY
ETHYLENE
HALOGENS
HYDROCARBONS
INFORMATION
MATHEMATICAL MODELS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
POTENTIAL ENERGY
RADICALS
STEREOCHEMISTRY
THEORETICAL DATA