Trisilaallene and the relative stability of Si3H4 isomers

Journal of Chemical Theory and Computation

Volumn 2, Issue 4, 2006, Pages 956-964

  Kosa, Monica ^a   Karni, Miriam ^a   Apeloig, Yitzhak ^a  

^a TECHNION ISRAEL INSTITUTE OF TECHNOLOGY   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33845928722     PISSN: 15499618     EISSN: None     Source Type: Journal    
DOI: 10.1021/ct050154a     Document Type: Article

References (68)

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42. A similar structure for trisilaallene was reported also by: Xu, W.; Yang, J.; Xiao, W. J. Phys. Chem. A 2004, 108, 11345-11353.
43. Kosa, M.; Karni, M.; Apeloig, Y. J. Am. Chem. Soc. 2004, 126, 10544. A very similar geometry was reported also in ref 10a.
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54. 2(3p) orbital in 6 is evident in the magnitude of the second-order perturbation stabilization energy (ΔE) resulting from this interaction. Thus, while ΔE is zero in 7 it increases to 177 kcal/mol in 6 (calculated using NBO 5.0). These interaction energies change significantly with the method of calculation and basis set used, but the same qualitative picture emerges with several used methods.
55. 2)) = 1.99 el., Table 2).
56. Fully optimized at UB3LYP/6-31G(d,p). The geometries are given in the Supporting Information.
57. 2-(3p) orbital. The different electronic structures of the triplet states of 6 and 7 point to the different electronic structures of the singlet ground states of 6 and 7.
58. 4 isomers were optimized also using the larger B3LYP/6-311G(2d,p) basis set. It was found that this does not change significantly their relative energies. There is a relatively good agreement between the relative energy of 12 with respect to 6, calculated at B3LYP/6-31G(d,p) (11.0 kcal/mol), MP2/6-31G(d,p) (8.5 kcal/mol), and CCSD/6-311+G(2df,p) (12.8 kcal/mol).
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67. 4 singlet surface.
68. While our paper was in press another paper that discusses the bonding in trisilaallene was published: Veszprémi, T.; Petrov, K.; Nguyen, C. T. Organometallics 2006, 25, 1480.