Issue 5, 1986

Experimental and theoretical studies on SiHn2+ dications (n= 1–5)1

Abstract

Ab initio molecular orbital calculations, executed at the MP4/6–31G**//6–31G* level, were performed for SiHn2+ dications (n= 1–5). In line with charge-stripping mass spectroscopic experiments both SiH2+ and SiH22+ are stable ions. Depending on the chemical precursor [i.e. Si(CH3)4 or SiH4] either the singlet ground state or the lowest triplet state of SiH+ are involved in the charge-stripping process. Moreover, electron impact ionization of SiH4 directly generates two stable states of SiH2+. For the system SiH2+–SiH22+, however, there is no experimental evidence for the involvement of excited states in the charge-stripping process. SiH32+ is also an experimentally accessible dication; however, the experimentally derived Qmin value and the theoretically predicted vertical ionization energy differ significantly for SiH32+, while they are in good to excellent agreement for SiH2+ and SiH22+, respectively. Owing to the lack of suitable cationic precursors no experimental data are available for SiH42+ and SiH52+. The calculations predict these species to be weakly bound complexes of SiH22+ and atomic and molecular hydrogen respectively.

Article information

Article type
Paper

J. Chem. Soc., Perkin Trans. 2, 1986, 757-760

Experimental and theoretical studies on SiHn2+ dications (n= 1–5)1

W. Koch, G. Frenking, H. Schwarz, F. Maquin and D. Stahl, J. Chem. Soc., Perkin Trans. 2, 1986, 757 DOI: 10.1039/P29860000757

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