Emission bands of SiCl2 and SnCl2

Asundi, R. K. ; Karim, M. ; Samuel, R. (1938) Emission bands of SiCl2 and SnCl2 Proceedings of the Physical Society, 50 (4). pp. 581-598. ISSN 0959-5309

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Official URL: http://iopscience.iop.org/0959-5309/50/4/310

Related URL: http://dx.doi.org/10.1088/0959-5309/50/4/310


The discharge through flowing vapour of SiCl4, SnCl4 and SnCl2 shows a number of regions of selective continuous emission, and, intimately connected with them, several sets of new bands. These appear under conditions unfavourable for the production of the known bands of SiCl and SnCl respectively. They are broad and diffuse, and have not the appearance of bands due to a diatomic emitter of low molecular weight. They are quite different from the known SiCl and SnCl bands as far as the anharmonic factor of the ground level of the molecule is concerned. They are therefore attributed to the triatomic molecules SiCl2 and SnCl2 respectively. An analysis carried out on this assumption reveals two excited electronic levels of SiCl2 (w = 28295 and 29952), and one of SnCl2 (v = 22237). The presence of the deforming (breathing) vibration ω1, and of the symmetrical valence vibration ω2 are indicated both in the ground state and in the various excited states. The antisymmetric valence vibration is absent, in agreement with Herzberg-Teller's selection rules. For certain reasons ω2' is smaller than ω2", despite ω' being larger than ω" in the corresponding excited terms of SiCl and SnCl. The energies of excitation and the values of ω2" of SiCl2 and SnCl2 show a close similarity to the corresponding constants of SiCl and SnCl respectively, and also the bond energies appear to be rather unaffected by the transition from the diatomic to the triatomic molecule. The later ones appear to be triangular.

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