Possible role for triplet H/sub 2/CN/sup +/ isomers in the formation of HCN and HNC in interstellar clouds
Journal Article
·
· J. Chem. Phys.; (United States)
OSTI ID:5051799
The structures and energies of the lowest triplet states of four isomers of H/sub 2/CN/sup +/ have been determined by self-consistent field and configuration interaction calculations. When both hydrogen atoms are attached to the nitrogen atom, H/sub 2/NC/sup +/, the molecule has its lowest triplet state energy, which is 97.2 kcal mol/sup -1/ above the energy of the linear singlet ground state. The structure has C/sub 2v/ symmetry, with an HCH bond angle of 116.8/sup 0/, and bond lengths of 1.009 A (H--N) and 1.268 A (N--C). Other isomers investigated include the H/sub 2/CN/sup +/ isomer at 104.7, the cis-HCNH/sup +/ isomer at 105.3, and the trans-HCNH/sup +/ isomer at 113.6 kcal mol/sup -1/. The H/sub 2/CN/sup +/ isomer has an unusual ''carbonium nitrene'' structure, with a C--N bond length of 1.398 A. It is suggested that the triplet H/sub 2/NC/sup +/ isomer may play a role in determining the relative yields of HCN and HNC from the reaction of C/sup +/ and NH/sub 3/. Specifically, a triplet path is postulated in which C/sup +/ and NH/sub 3/ yield the triplet H/sub 2/NC/sup +/ isomer, which then yields the singlet H/sub 2/NC/sup +/ isomer by phosphorescent emission. Because this emission removes a large amount of energy, the singlet H/sub 2/NC/sup +/ isomer may have insufficient energy to isomerize to the linear singlet ground state. Subsequent dissociative recombination would yield the HNC isomer exclusively.
- Research Organization:
- Department of Chemistry, University of California, Davis, California 95616
- OSTI ID:
- 5051799
- Journal Information:
- J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 73:7; ISSN JCPSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
CHEMICAL REACTIONS
CONFIGURATION INTERACTION
COSMIC GASES
CYANIDES
DATA
ENERGY LEVELS
EXCITED STATES
FLUIDS
GASES
HYDROCYANIC ACID
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
INTERSTELLAR GRAINS
ISOMERIZATION
MOLECULAR STRUCTURE
NUMERICAL DATA
PARTICLES
SELF-CONSISTENT FIELD
THEORETICAL DATA
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
CHEMICAL REACTIONS
CONFIGURATION INTERACTION
COSMIC GASES
CYANIDES
DATA
ENERGY LEVELS
EXCITED STATES
FLUIDS
GASES
HYDROCYANIC ACID
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
INTERSTELLAR GRAINS
ISOMERIZATION
MOLECULAR STRUCTURE
NUMERICAL DATA
PARTICLES
SELF-CONSISTENT FIELD
THEORETICAL DATA