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Some Propensity Rules in Collision‐Induced Rotational Quantum Jumps
1.B. Stevens, The International Encyclopedia of Physical Chemistry and Chemical Physics (Pergamon Press Ltd., Oxford, England, 1967), Vol. 3, “Collisional Activation in Gases.”
1.R. G. Gordon, W. Klemperer, and J. I. Steinfield, Ann. Rev. Phys. Chem. 19, 215 (1968).
2.T. Carrington, J. Chem. Phys. 31, 1418 (1959);
2.in Symp. Combust. 8th, 1257 (1960).
3.H. P. Broida and T. Carrington, J. Chem. Phys. 38, 136 (1963).
4.J. I. Steinfeld and W. Klemperer, J. Chem. Phys. 42, 3475 (1965).
5.D. L. Akins and C. B. Moore, Bull. Am. Phys. Soc. 11, 889 (1966).
6.R. Velasco, Ch. Ottinger, and R. N. Zare, J. Chem. Phys. 51, 5522 (1969).
7.A classical explanation for this phenomena is as follows: The collision causes J to change without altering appreciably the M state distribution. The radiation is thus of the type or whose degree of polarization in the limit of large J is [See R. N. Zare, J. Chem. Phys. 45, 4510 (1966)].
7.Analogous polarization differences have been observed in by W. Demtröder and M. McClintock (private communication).
8.See G. Herzberg, Spectra of Diatomic Molecules (D. Van Nostrand Co., Inc., Princeton, N.J., 1950), pp. 130–140. For homonuclear diatomics having no nuclear spin the prohibition of intercombinations between symmetric and antisymmetric levels is perfectly rigorous.
8.For the molecule composed of nuclei with spin three‐halves this selection rule no longer holds absolutely since there is the possibility of collisions that simultaneously alter the rotational and nuclear‐spin states. However, such interconversions are extremely rare. See the work of G. W. Flynn and J. D. Baldeschwieler, J. Chem. Phys. 37, 2907 (1962) on the measurement of the relaxation rate of equivalent F atoms in the gas phase.
9.If the two nuclei in a diatomic molecule have the same charge, as in and in the force field in which the electrons move has a center of symmetry. The electronic eigenfunctions are then classified by g or u depending on whether or not they remain unchanged or change sign under inversion through this center. See. Ref. 8, pp. 217–218.
10.The radiative lifetime of the state is presently unknown. However, if we assume its behavior is comparable to the state of [See M. McClintock, W. Demtröder, and R. N. Zare, J. Chem. Phys. 51, 5509 (1969)]
10.or the state of [See W. J. Tango, J. K. Link, and R. N. Zare, J. Chem. Phys. 49, 4264 (1968)],
10.the molecular radiative lifetime will be less than the parent Li 2p atom, i.e., less than [See W. S. Bickel, I. Martinson, L. Lundin, R. Buchta, J. Bromander, and I. Bergström, J. Opt. Soc. Am. 59, 830 (1969)].
11.For a more complete treatment see R. de L. Kronig, Band Spectra and Molecular Structure (Cambridge University Press, Cambridge, England, 1930);
11.L. D. Landau and E. M. Lifshitz, Quantum Mechanics (Addison‐Wesley Publ. Co., Inc., Reading, Mass., 1958), Chap. XI.
12.C. H. Townes and A. L. Schawlov, Microwave Spectroscopy (McGraw‐Hill Book Co., New York, 1955).
13.For a review of theoretical studies of rotational transfer in molecular collisions see K. Takayanagi in Advances in Atomic and Molecular Physics, D. R. Bates and I. Estermann, Eds. (Academic Press Inc., New York, 1965).
14.Such calculations have been performed by R. J. Cross, Jr. and D. R. Herschbach, J. Chem. Phys. 43, 3530 (1965).
15.E. A. Mason, J. T. Vanderslice, and J. M. Yos, Phys. Fluids 2, 688 (1959);
15.L. Monchik and E. A. Mason, J. Chem. Phys. 35, 1676 (1961);
15.L. Monchik and E. A. Mason, 36, 2746 (1962)., J. Chem. Phys.
16.Of course if certain other features of the collision interaction are present, such as long range dipole‐dipole forces, they may predominate over the propensities we have discussed.
17.See B. J. Robinson and R. X. McGee, Ann. Rev. Astron. Astrophys. 5, 183 (1967).
18.For a discussion of l‐type doubling, consult H. C. Allen, Jr. and P. C. Cross, Molecular Vib‐Rotors (John Wiley & Sons, Inc., New York, 1963).
18.See also T. Oka, J. Chem. Phys. 47, 5410 (1967).
19.Considerable progress has been made in elucidating the rotational transfer propensities of ground‐state polyatomics through the method of microwave double resonance, when it is applicable. See A. P. Cox, G. W. Flynn, and E. B. Wilson, Jr., J. Chem. Phys. 42, 3094 (1965);
19.T. Oka, J. Chem. Phys. 45, 754 (1966); , J. Chem. Phys.
19.T. Oka, 47, 13 (1967); , J. Chem. Phys.
19.T. Oka, 47, 4852 (1967); , J. Chem. Phys.
19.T. Oka, 48, 4919 (1968); , J. Chem. Phys.
19.T. Oka, 49, 3135 (1968); , J. Chem. Phys.
19.T. Oka, 49, 4234 (1968); , J. Chem. Phys.
19.A. M. Ronn and E. B. Wilson, Jr., J. Chem. Phys. 46, 3262 (1967); , J. Chem. Phys.
19.R. G. Gordon, P. E. Larson, C. H. Thomas, and E. B. Wilson, Jr., J. Chem. Phys. 50, 1388 (1969)., J. Chem. Phys.
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