The electronic state‐selective photodissociation of CH2BrI at 248, 210, and 193 nm
1.S. J. Lee and R. Bersohn, J. Phys. Chem. 86, 728 (1982).
2.D. Krajnovich, L. J. Butler, and Y. T. Lee, J. Chem. Phys. 81, 3031 (1984).
3.L. Cavalli, J. Magn. Reson. 6, 298 (1972).
4.The heats of formation of a variety of chemical species used to calculate the enthalpies shown in Fig. 1 were obtained from: H. M. Rosenstock, K. Draxl, B. W. Steiner, and J. T. Herron, J. Phys. Chem. Ref. Data 6, Suppl. 1, I‐774 (1977).
4.The heat of formation of 17.338 kcal/mol at 0 K, is calculated in S. A. Kudchadker and A. P. Kudchadker, J. Phys. Chem. Ref. Data 7, 1285 (1978). In addition, the C‐I and C‐Br bond fission energies in were assumed to be the same as in and respectively. Calculation of the HI and HBr elimination channel endoergicities also required the assumption that the energy required to remove H from or is the same as required to remove it from C‐H bond fission and elimination are not included as we are not sensitive to these channels in our experiment.
5.ONR/NRL Workshop on Energetic Materials Initiation Fundamentals, October 30–November 1 1984.
6.L. J. Butler, Ph.D. thesis, University of California, Berkeley 1985.
7.This is a result of both sets of products recoiling down a similar repulsive energy surface except for the difference in final product energies. The complete or partial resolution in TOF spectra of products from carbon‐halogen bond fission producing two spin‐orbit states of halogen atom product has been previously observed by several workers cited in Ref. 6.
8.M. D. Barry and P. A. Gorry, Mol. Phys. 52, 461 (1984).
9.D. Krajnovich, Z. Zhang, L. Butler, and Y. T. Lee, J. Phys. Chem. 88, 4561 (1984).
10.R. N. Zare, Mol. Photochem. 4, 1 (1972).
11.Y. B. Band, K. F. Freed, and S. J. Singer, J. Chem. Phys. 84, 3762 (1986), and references by Band, Freed, et al. within.
12.D. J. Krajnovich, Ph.D. thesis, University of California, Berkeley, California, Appendix B, 1983.
13. for the state of IBr is obtained from K. P. Huber and G. Herzberg, Molecular Spectra and Molecular Structure IV: Constants of Diatomic Molecules (Van Nostrand Reinhold, New York, 1979).
14.This work was published in preliminary form as a communication. L. J. Butler, E. J. Hintsa, and Y. T. Lee, J. Chem. Phys. 84, 4104 (1986).
15.(a) See Ref. 27;
15.(b) M. S. Child and R. B. Bernstein, J. Chem. Phys. 59, 5916 (1973).
16.(a) P. J. Robinson and K. A. Holbrook, Unimolecular Reactions (Wiley‐Interscience, New York, 1972);
16.(b) I. W. M. Smith, Kinetics and Dynamics of Elementary Gas Reactions (Butterworths, London, 1980).
17.F. F. Crim, Annu. Rev. Phys. Chem. 35, 657 (1984).
18.(a) J. G. Calvert and J. N. Pitts, Jr., Photochemistry (Wiley, New York, 1966), Chap. 5, pp. 522–528; (b) R. P. Wayne, Photochemistry (Elsevier, New York, 1970), Chap. 3, pp. 66–67.
19.See Calvert and Pitts of Ref. 18, Chap. 5, p. 526.
20.Electronic levels in iodoalkanes are derived with analogy to HI, see R. S. Mulliken, Phys. Rev. 51, 310 (1936),
20.related papers, and Phys. Rev. 47, 413 (1935) as well as the review given in Ref. 2., Phys. Rev.
21.J. T. Yardley, Introduction to Molecular Energy Transfer (Academic, New York, 1980).
22.Transitions dipole moments to the surfaces of the transitions are parallel to each bond (Ref. 20) and the C‐I and C‐Br bonds are parallel to each other before the Franck‐Condon excitation. The molecules are cooled in the expansion and the molecular ground state is lowest in energy in the trans configuration by 1.15 kcal/mol according to Ref. 3.
23.J. P. Simons and A. J. Yarwood, Nature 192, 943 (1961).
24.W. H. Pence, S. L. Baughcum, and S. R. Leone, J. Phys. Chem. 85, 3844 (1981).
25.D. W. G. Style and J. C. Ward, J. Chem. Soc. 1952, 2125.
26.The description is analogous to the least motion reaction path shown for a more restricted case where the two halogens have the same identity and the initial transition is not localized on one of the bands by S. R. Cain, R. Hoffman, and E. R. Grant, J. Phys. Chem. 85, 4046 (1981).
27.G. N. A. van Veen, Ph.D. thesis, FOM Institute of Atomic and Molecular Physics, Amsterdam, 1984.
28.G. E. Busch and K. R. Wilson, J. Chem. Phys. 56, 3626 (1972).
29.Such a result was first suggested in Ref. 1 and selective fission of the C‐H bond over the C‐I bond in was observed by M. R. Levy and J. P. Simons, J. Chem. Soc. Faraday Trans. 2 71, 561 (1975).
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