Si2CN: a stable nitrogen-containing radical with cyclic ground state.
The structures and isomerization of Si(2)CN species are explored at density functional theory and ab initio levels. Fourteen minimum isomers are located connected by 23 interconversion transition states. At the coupled-cluster single double (CCSD)(T)/6-311+G(2df)//QCISD/6-311G(d) +zero-point vibrational energies level, the thermodynamically most stable isomer is a four-membered ring form cSiSiCN 1 with Si-C cross bonding. Isomer 1 has very strong C-N multiple bonding characters, formally suggestive of a radical adduct between Si(2) and CN. Such a highly pi-electron localization can effectively stabilize isomer 1 to be the ground state. The second low-lying isomer is a linear form SiCNSi 5 (9.8 kcal/mol above 1) with resonating structure among [Si=C-*N=Si], *[Si=C=N=Si], and [Si=C=N-Si*]* with the former two bearing more weight. The species 1 and 5 have very high kinetic stability stabilized by the barriers of at least 25 kcal/mol. Both isomers should be experimentally or astrophysically observable. In light of the fact that no cyclic nitrogen-containing species have been detected in space, the cyclic species 1 could be a very promising candidate. The calculated results are compared to those of the analogous molecules C(3)N, C(3)P, SiC(2)N, and SiC(2)P. Implications of Si(2)CN in interstellar and N-doped SiC vaporization processes are also discussed.
Chen
Guang-Hui
GH
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China.
Ding
Yi-Hong
YH
Huang
Xu-Ri
XR
Yu
Jian-Kang
JK
Sun
Chia-Chung
CC