Thermodynamic calculations for molecules with asymmetric internal rotors. II. Application to the 1,2-dihaloethanes

✍ Scribed by Bryan M. Wong; Maria M. Fadri; Sumathy Raman

• Publisher: John Wiley and Sons
• Year: 2007
• Tongue: English
• Weight: 277 KB
• Volume: 29
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.20807

✦ Synopsis

Abstract

The thermodynamic properties of three halocarbon molecules relevant in atmospheric and public health applications are presented from ab initio calculations. Our technique makes use of a reaction path‐like Hamiltonian to couple all the vibrational modes to a large‐amplitude torsion for 1,2‐difluoroethane, 1,2‐dichloroethane, and 1,2‐dibromoethane, each of which possesses a heavy asymmetric rotor. Optimized ab initio energies and Hessians were calculated at the CCSD(T) and MP2 levels of theory, respectively. In addition, to investigate the contribution of electronically excited states to thermodynamic properties, several excited singlet and triplet states for each of the halocarbons were computed at the CASSCF/MRCI level. Using the resulting potentials and projected frequencies, the couplings of all the vibrational modes to the large‐amplitude torsion are calculated using the new STAR‐P 2.4.0 software platform that automatically parallelizes our codes with distributed memory via a familiar MATLAB interface. Utilizing the efficient parallelization scheme of STAR‐P, we obtain thermodynamic properties for each of the halocarbons, with temperatures ranging from 298.15 to 1000 K. We propose that the free energies, entropies, and heat capacities obtained from our methods be used to supplement theoretical and experimental values found in current thermodynamic tables. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2008