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Molecular Rydberg transitions. XX. Vibronic doubling in alkyl bromides
1.R. S. Mulliken, Phys. Rev. 57, 500 (1940).
2.S. P. McGlynn, J. D. Scott, W. S. Felps, and G. L. Findley, J. Chem. Phys. 72, 421 (1980).
3.N. L. Baker and B. R. Russell, J. Mol. Spectrosc. 69, 211 (1978). These authors provide a rather complete literature survey.
4. possesses six normal modes Two of these, symmetric stretch) and (e, HCBr angle deformation), are of importance in the present work. The normal modes of are discussed in Ref. 5. possesses 18 normal modes. These are discussed by S. Suzuki, J. L. Bribes, and R. Gaufrés, J. Mol. Spectrosc. 47, 118 (1973)
4.for both and We number these modes starting from top of Table III of this source. The normal modes of relevance to the present work are Modes through are totally symmetric the remainder are Modes and are particularly relevant to vibronic coupling; is observed as progressions built on both origins 2 and 4; and are important relative to hot band occurrences off origin 1; is observed as progressions built on 1, 2, and 4; and is important relative to coupling. possesses 27 normal modes. These are discussed by M. Hayashi, K. Ohno, and H. Murata, Bull. Chem. Soc. Jpn. 46, 2332 (1973).
5.S. Felps, P. Hochmann, P. Brlnt, and S. P. McGlynn, J. Mol. Spectrosc. 59, 355 (1976).
6.The zero‐order transitions to α; or 3, will always be of much lower intensity than that to state 4. Since α; is presumed to obtain its intensity by “stealing” from 4, it would require rather unusual circumstances to have the lower‐intensity component of the doublet contain more 4 than α; character. Consequently, the lower‐intensity doublet (which is also always of lower energy) is attributed to the α; ‐rich component.
7.S. P. McGlynn, W. S. Felps, J. D. Scott, and G. L. Findley, J. Chem. Phys. 73, 4925 (1980). The nature of the vibronic operator, with particular emphasis on its symmetry properties, is also discussed in this work.
8.For example, the ‐set in which we use the difference of ionization potentials
9.S. P. McGlynn, W. S. Felps, and J. Daigneault (in preparation).
10.W. S. Felps, G. L. Findley, and S. P. McGlynn, Chem. Phys. Lett. (in press).
11.A. C. Albrecht, J. Chem. Phys. 38, 354 (1963);
11.and A. H. Kalantar, and A. C. Albrecht, Ber. Bunsengesell. Physik. Chem. 68, 377 (1964).
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