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Lifetimes and Quantum Yields of Individual Vibronic States of C6D6 and C6H5F
1.K. G. Spears and S. A. Rice, J. Chem. Phys. 55, 5561 (1971).
2.W. Gelbart, K. G. Spears, K. F. Freed, J. Jortner, and S. A. Rice, Chem. Phys. Letters 6, 345 (1970).
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5.D. F. Heller, K. F. Freed, and W. M. Gelbart, J. Chem. Phys. 56, 2309 (1972), following paper.
6.See Table VIII.
7.See Table IX.
8.The value of was obtained from independent measurements of the absorption strength of a transition assuming the validity of the Beer‐Lambert law. Unlike the corresponding measurements for the values of the extinction coefficient ε for and exhibited slight pressure dependences. The inferred values of ε often varied inversely with pressure in a nonlinear fashion; attempts to identify and eliminate systematic sources of error in the apparatus were not fruitful.
8.Others have also found behavior of this type: in in the same pressure range [G. B. Kistiakowsky and C. S. Parmenter, J. Chem. Phys. 42, 2942 (1965)],
8.and in monofluorobenzene at higher pressures [I. Unger, J. Phys. Chem. 69, 4284 (1968);
8.H. E. MacBeath, G. P. Semeluk, and I. Unger, J. Phys. Chem. 73, 995 (1969)]. We have made all our calculations with values of ε determined at pressures as close as possible to those used in the corresponding lifetime experiments. The deviations of the values of e from constancy are not large: 8% in and 3% in
9.See, for example, J. B. Birks, Phys. Rev. 94, 1567 (1964).
10.Molecular parameters determined using only the third to fifth decades of the decay of the emission were compared with those determined from deconvolution of the entire decay curve for the strongest emitting states of Both schemes led to the same values of the molecular parameters within the experimental precision.
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24.D. H. Brown, A. Mohammed, and D. W. A. Sharp, Spectrochim. Acta 21, 659 (1965).
25.S. C. Sirkar, D. K. Mukherjee, and P. K. Bishui, Indian J. Phys. 38, 610 (1964);
25.S. C. Sirkar and P. K. Bishui, Indian J. Phys. 42, 1 (1968)., Indian J. Phys.
26.I. A. Zhigunova, Opt. Spectrosk. 26, 173 (1969)
26.[I. A. Zhigunova, Opt. Spectrosc. 26, 93 (1969)].
27.E. B. Wilson, Phys. Rev. 45, 706 (1934).
28.K. S. Pitzer and D. W. Scott, J. Am. Chem. Soc. 65, 803 (1943).
29.E. B. Wilson, J. C. Decius, and P. C. Cross, Molecular Vibrations (McGraw‐Hill, New York, 1955).
30.K. Nakamura, J. Chem. Phys. 53, 988 (1970).
31.W. A. Noyes, Jr., W. A. Mulac, and D. A. Harker, J. Chem. Phys. 44, 2100 (1966).
32.See, for example, G. Herzberg, Electronic Spectra of Polyatomic Molecules (Van Nostrand, New York, 1966).
33.A good review is contained in C. S. Parmenter, Advan. Chem. Phys. 22, 365 (1972).
34.S. H. Lin, J. Chem. Phys. 44, 3759 (1966);
34.M. Bixon and J. Jortner, J. Chem. Phys. 48, 715 (1968); , J. Chem. Phys.
34.K. F. Freed and J. Jortner, J. Chem. Phys. 52, 6272 (1970); , J. Chem. Phys.
34.D. M. Burland and G. W. Robinson, J. Chem. Phys. 51, 4548 (1969); , J. Chem. Phys.
34.D. M. Burland and G. W. Robinson, Proc. Natl. Acad. Sci. U.S. 66, 257 (1970);
34.B. R. Henry and W. Siebrand, J. Chem. Phys. 54, 1072 (1971);
34.R. Lefebvre, Chem. Phys. Letters 8, 306 (1971);
34.K. F. Freed, “The Theory of Radiationless Processes in Polyatomic Molecules,” Topics Current Chem. (to be published);
34.K. F. Freed and W. M. Gelbart, Chem. Phys. Letters, 10, 187 (1971).
35.See Ref. 1, Eq. (14).
36.For a detailed study, see B. R. Henry and W. Siebrand, J. Chem. Phys. 54, 1072 (1971).
37.A. Nitzan and J. Jortner, J. Chem. Phys. 55, 1355 (1971).
38.K. F. Freed (private communication); see also Ref. 5.
39.K. F. Freed informs us that5 the difficulty in the Nitzan‐Jortner analysis, as applied to benzene, is that they require 〈γ〉 to be, simultaneously, much less than and much greater than Indeed, the Nitzan‐Jortner prediction concerning the promoting mode behavior is only valid when For most instances in which the energy gap law is valid this limit is not obtained. For the case excitation of the promoting mode leads to lifetimes that vary as instead of as predicted by Nitzan and Jortner. For benzene and then so that
40.H. Von Weyssenhoff and F. Krauss, J. Chem. Phys. 54, 2387 (1971).
41.C. S. Parmenter and A. H. White, J. Chem. Phys. 50, 1631 (1969).
42.See Ref. 1 for a discussion of the Parmenter and White collision cross sections.
43.G. B. Kistiakowsky and C. S. Parmenter, J. Chem. Phys. 42, 2942 (1965).
44.E. Anderson and G. B. Kistiakowsky, J. Chem. Phys. 48, 4787 (1968);
44.E. Anderson and G. B. Kistiakowsky, 51, 182 (1969)., J. Chem. Phys.
45.C. W. Mathews and A. E. Douglas, J. Chem. Phys. 48, 4788 (1968).
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