Ab initio studies of internal rotation barriers and vibrational frequencies of (C2H2)2, (CO2)2, and C2H2-CO2

1991 ◽  
Vol 78 (3) ◽  
pp. 133-163 ◽  
Author(s):  
Richard G. A. Bone ◽  
Nicholas C. Handy
Keyword(s):  
Ab Initio ◽  
Internal Rotation ◽  
Vibrational Frequencies

An ab initio study of the structures, barriers for internal rotation, vibrational frequencies, and thermodynamic functions of the hydrochlorofluorocarbon CH3CF2Cl and the corresponding radical CH2CF2Cl

1994 ◽  
Vol 72 (3) ◽  
pp. 561-567 ◽  
Author(s):  
S.J. Paddison ◽  
Yonghua Chen ◽  
E. Tschukow-Roux
Keyword(s):  
Ab Initio ◽  
Internal Rotation ◽  
Vibrational Energy ◽  
Zero Point ◽  
Heat Of Formation ◽  
Vibrational Frequencies ◽  
Radical Center ◽  
Molecular Orbital Calculations ◽  
Parent Molecule ◽  
Moller Plesset

Ab initio molecular orbital calculations were performed using the GAUSSIAN 90 system of programs at the HF/6-31G* level of theory, on the hydrochlorofluorocarbon (HCFC) 1-chloro-1,1-difluoroethane and the 1-chloro-1,1-difluoroethyl radical. Equilibrium geometries, barriers for internal rotation, and harmonic vibrational frequencies were thus calculated. A single conformational minimum in the potential energy surface was located for both the radical and the parent molecule. The radical center in CH2CF2Cl was found to be nonplanar. Transition structures for internal rotation about the C—C bond were located for both the molecule and the radical using analytical methods. The rotation barriers, evaluated at the fourth-order Møller–Plesset perturbation theory ((U)MP4/6-311G**/6-31G*). were calculated after inclusion of zero-point vibrational energy differences to be 1.11 and 4.12 kcal/mol for the radical and the parent molecule, respectively. Computed thermodynamic properties including heat capacity, entropy, enthalpy, and free energy functions are reported as a function of temperature. Using an experimentally measured heat of formation of CH3CF2Cl at 298 K, the heat of formation of CH2CF2Cl was calculated to be −74.3 ± 1.7 kcal/mol. Tabulations of ΔH0f,T, ΔG0f,T, and log10Kf,T over the temperature range of 0–1500 K are also reported for both species.

Sign in / Sign up

Export Citation Format

Share Document