A possible role for triplet H2CN+ isomers in the formation of HCN and HNC in interstellar clouds
- Univ. of California, Davis, CA (United States)
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
We determine the structures and energies of the lowest triplet states of four isomers of H2CN+ by self-consistent field and configuration interaction calculations. When both hydrogen atoms are attached to the nitrogen atom, H2CN+, the molecule has its lowest triplet state energy, which is 97.2 kcal mol-1 above the energy of the linear singlet ground state. The structure has C2v symmetry, with an HCH bond angle of 116.8°, and bond lengths of 1.009 Å (H–N) and 1.268 Å (N–C). Other isomers investigated include the H2CN+ isomer at 104.7, the c i s-HCNH+ isomer at 105.3, and the t r a n s-HCNH+ isomer at 113.6 kcal mol-1. The H2CN+ isomer has an unusual ’’carbonium nitrene’’ structure, with a C–N bond length of 1.398 Å. It is suggested that the triplet H2CN+ isomer may play a role in determining the relative yields of HCN and HNC from the reaction of C+ and NH3. Specifically, a triplet path is postulated in which C+ and NH3 yield the triplet H2NC+ isomer, which then yields the singlet H2CN+ isomer by phosphorescent emission. Furthermore, because this emission removes a large amount of energy, the singlet H2CN+ isomer may have insufficient energy to isomerize to the linear singlet ground state. Subsequent dissociative recombination would yield the HNC isomer exclusively.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- DOE Contract Number:
- AC02-05CH11231; W-7405-ENG-48
- OSTI ID:
- 1133679
- Report Number(s):
- LBL-11923; JCPSA6
- Journal Information:
- Journal of Chemical Physics, Vol. 73, Issue 7; ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
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