Geometrical structures, bending potentials, and vibrational frequencies ν1 for 1A″ states of HSiBr, HSiCl, and DSiCl

Resolution of anomalies in the geometry and vibrational frequencies of monobromosilylene (HSiBr) by pulsed discharge jet spectroscopy

“…The spectrum of HSiBr is very simple, consisting of a long progression ͑up to 2 0 5 ͒ of intense bands involving the bending levels, a very weak 3 0 1 band, and some weak combination bands. The previously unobserved 1 0 1 band occurs 1787 cm Ϫ1 above the 0 0 0 band, providing a value for 1 Ј in accord with the alternative assignment of H&V, supported by the bending potential calculations of Gilchrist et al 13 The spectrum of DSiBr, which was not studied by H&V, is much more complex than that of HSiBr, as illustrated in Fig. 1.…”

“…In further work, Gilchrist et al 13 determined the excited state geometry and bending potential of HSiBr by fitting the H&V data to a rigid bender model. They obtained very similar geometric parameters, but concluded that 1 Ј ϭ 1785 cm Ϫ1 , rather than the 1270 cm Ϫ1 value preferred in the previous work.…”

Ab Initio Potential Energy Surfaces for Both the Ground (X̃1A′) and Excited (ALi1, Lin2, Xie3 2012Advances in Physical Chemistry33040View full textAdd to dashboardCite

“…Unlike HSiF and HSiCl, only a few theoretical studies have been reported for monobromosilylene (HSiBr) [6,13]. In 1979, Gilchrist et al [6] determined the geometrical structures and bending potentials for the excited state A 1 A of HSiBr by fitting the Herzberg and Verma's data [3] and also obtained the H-Si stretching frequency(ν 1 which is agreement with the later experimental value of 1787 cm −1 [8].…”

“…The identification and quantification of such intermediates could help make these processes more efficient, so that they have attracted much attention in experimental and theoretical studies [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. However, because these radicals are typically short-lived and highly reactive, it is difficult to monitor them.…”

“…In 1979, Gilchrist et al [6] determined the geometrical structures and bending potentials for the excited state A 1 A of HSiBr by fitting the Herzberg and Verma's data [3] and also obtained the H-Si stretching frequency(ν 1 which is agreement with the later experimental value of 1787 cm −1 [8]. In order to ascertain the validity of their refined force constants, Hostutler et al [13] calculated the independent ground and excited state structures at B3LYP level with 6-311G(3df,3pd) basis set in 2001.…”