Charge-transfer complexes. NH/sub 3/--O/sub 3/, NH/sub 3/--SO/sub 2/, and N(CH/sub 3/)/sub 3/--SO/sub 2/
The donor--acceptor complex between trimethylamine and sulfur dioxide is the strongest (in terms of its dissociation energy to N(CH/sub 3/)/sub 3/ plus SO/sub 2/) such complex yet to be studied experimentally in the gas phase. Ab initio self-consistent-field theory has been applied to this and two related complexes, NH/sub 3/O/sub 3/ and NH/sub 3/SO/sub 2/. Minimum basis sets were used for all three complexes, while for NH/sub 3/SO/sub 2/ two considerably larger sets (double zeta and double zeta plus sulfur d functions) were employed. The equilibrium structure of these complexes was predicted by an investigation of many points on the respective potential energy surface. To a surprising degree, the O/sub 3/ or SO/sub 2/ molecule is found to lie in a plane nearly perpendicular to ttthe amine C/sub 3v/ axis. Further, the central atom in O/sub 3/ and SO/sub 2/ is predicted to lie only slighty off the amine C/sub 3v/ axis. With these guidelines, the prediction of further structures of this type essentially reduces a one-dimensional search for the central atom-N distance. Using a minimum basis set, the three predicted binding energies at 2.24, 5.00, and 4.06 kcal/mole. Using the double zeta basis set the NH/sub 3/--SO/sub 2/ dissociation energy is increased to 10.40 kcal/mole. When a set of sulfur d functions is added to the latter set, the binding energy becomes 9.30 kcal/mole in the absence of geometry reoptimization.
- Research Organization:
- Univ. of California, Berkeley
- OSTI ID:
- 7232170
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 98:24; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Potential energy surfaces for ion-molecule reactions. Intersection of the /sup 3/A/sub 2/ and /sup 2/B/sub 1/ surfaces of NH/sup +//sub 2/
Theoretical study of the properties of BH/sub 3/NH/sub 3/
Related Subjects
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
AMINES
AMMONIA
ATOMIC MODELS
BINDING ENERGY
BOND ANGLE
BOND LENGTHS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
ENERGY
EQUILIBRIUM
GAS ANALYSIS
HYDRIDES
HYDROGEN COMPOUNDS
MATHEMATICAL MODELS
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
OZONE
SELF-CONSISTENT FIELD
STRUCTURAL CHEMICAL ANALYSIS
SULFUR COMPOUNDS
SULFUR DIOXIDE
SULFUR OXIDES