Journal article
Methyl cation affinities of rare gases and nitrogen and the heat of formation of diazomethane
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.109(18), pp.4073-4080
05/12/2005
Handle:
https://hdl.handle.net/2376/112763
PMID: 16833729
Abstract
The methyl cation affinities of the rare gases have been calculated at 0 and 298 K by using coupled cluster theory including noniterative, quasiperturbative triple excitations with the new correlation-consistent basis sets for Xe up through aug-cc-pV5Z in some cases. To achieve near chemical accuracy (+/-1 kcal/mol) in the thermodynamic properties, we add to the estimated complete basis set valence binding energies, based on frozen core coupled cluster theory energies, two corrections: (1) a core/valence correction and (2) a scalar relativistic correction. Vibrational zero-point energies were computed at the coupled cluster level of theory at the CCSD(T)/aug-cc-pVDZ level. The calculated rare gas methyl cation affinities (MCA in kcal/mol) at 298 K are the following: MCA(He) = 1.7, MCA(Ne) = 2.5, MCA(Ar) = 16.9, MCA(Kr) = 25.5, and MCA(Xe) = 36.6. Because of the importance of the MCA(N(2)) in the experimental measurements of the MCA scale, we calculated a number of quantities associated with CH(3)N(2)(+) and CH(2)N(2). The calculated values for diazomethane at 298 K are: DeltaH(f)(CH(2)N(2)) = 65.3 kcal/mol, PA(CH(2)N(2)) = 211.9 kcal/mol, and MCA(N(2)) = 43.2 kcal/mol.
Metrics
5 Record Views
Details
- Title
- Methyl cation affinities of rare gases and nitrogen and the heat of formation of diazomethane
- Creators
- David A Dixon - Department of Chemistry, Shelby Hall, P.O. Box 870336, University of Alabama, Tuscaloosa, Alabama 35487-0336, USA. dadixon@bama.ua.eduWibe A de JongKirk A PetersonTerrance B McMahon
- Publication Details
- The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.109(18), pp.4073-4080
- Academic Unit
- Chemistry, Department of
- Publisher
- United States
- Identifiers
- 99900548162301842
- Language
- English
- Resource Type
- Journal article