Isotope effects in the vibrational deactivation of large molecules
dc.contributor.author | Toselli, Beatriz M. | en_US |
dc.contributor.author | Barker, John R. | en_US |
dc.date.accessioned | 2010-05-06T21:19:31Z | |
dc.date.available | 2010-05-06T21:19:31Z | |
dc.date.issued | 1992-08-01 | en_US |
dc.identifier.citation | Toselli, Beatriz M.; Barker, John R. (1992). "Isotope effects in the vibrational deactivation of large molecules." The Journal of Chemical Physics 97(3): 1809-1817. <http://hdl.handle.net/2027.42/69901> | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/69901 | |
dc.description.abstract | Collisional deactivation of highly vibrationally excited gas phase toluene‐d8 and benzene‐d6 pumped at 248 nm, has been investigated by monitoring the time resolved infrared fluorescence from the C–D stretch modes near 4.3 μm. For toluene‐d8, energy transfer data were obtained for about 20 collider gases, including unexcited toluene‐d8; for benzene‐d6, only a few colliders were investigated. For both systems the data were analyzed by an inversion technique that converts the fluorescence decay to the bulk average energy, from which is calculated the average energy transferred per collision, 〈〈ΔE〉〉inv. Data obtained earlier for benzene‐d0 were reanalyzed and the revised results are reported. Results for both normal and deuterated excited species show 〈〈ΔE〉〉inv to be nearly directly proportional to the vibrational energy 〈〈E〉〉inv of the excited molecule from 5 000 to 25 000 cm−1. However, for pure toluene‐d8, benzene‐d6, and a few other collider gases at high energies, the slope of the 〈〈ΔE〉〉inv vs 〈〈E〉〉inv curve is reduced and even becomes negative at sufficiently high energies. The results obtained for normal and deuterium‐containing species are discussed in terms of possible quantum effects and mechanisms for energy transfer. In particular, it is considered likely that V–T/R energy transfer dominates over V–V, and the lowest frequency vibrational modes are the conduits for the energy transfer, in agreement with results for small molecules. Attention is called to a fundamental difference between classical and quantum statistics and how this difference may adversely affect classical trajectory simulations of large molecules. | en_US |
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dc.format.extent | 1197016 bytes | |
dc.format.mimetype | text/plain | |
dc.format.mimetype | application/pdf | |
dc.publisher | The American Institute of Physics | en_US |
dc.rights | © The American Institute of Physics | en_US |
dc.title | Isotope effects in the vibrational deactivation of large molecules | en_US |
dc.type | Article | en_US |
dc.subject.hlbsecondlevel | Physics | en_US |
dc.subject.hlbtoplevel | Science | en_US |
dc.description.peerreviewed | Peer Reviewed | en_US |
dc.contributor.affiliationum | Department of Atmospheric, Oceanic, and Space Sciences, Department of Chemistry, Space Physics Research Laboratory, The University of Michigan, Ann Arbor, Michigan 48109‐2143 | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/69901/2/JCPSA6-97-3-1809-1.pdf | |
dc.identifier.doi | 10.1063/1.463168 | en_US |
dc.identifier.source | The Journal of Chemical Physics | en_US |
dc.identifier.citedreference | For a recent review, see I. Oref and D. C. Tardy, Chem. Rev. 30, 1407 (1990). | en_US |
dc.identifier.citedreference | (a) M. J. Rossi, J. R. Pladziewicz, and J. R. Barker, J. Chem. Phys. 78, 6695 (1983), and references therein; (b) J. R. Barker, J. Phys. Chem. 88, 11 (1984); (c) J. R. Barker and R. E. Golden, 88, 1012 (1984). | en_US |
dc.identifier.citedreference | J. Shi and J. R. Barker, J. Chem. Phys. 88, 6219 (1988); J. Shi, D. Bern-feld, and J. R. Barker, 88, 6211 (1988). | en_US |
dc.identifier.citedreference | J. M. Zellweger, T. C. Brown, and J. R. Barker, J. Chem. Phys. 83, 6261 (1985). | en_US |
dc.identifier.citedreference | M. L. Yerram, J. D. Brenner, K. D. King, and J. R. Barker, J. Phys. Chem. 94, 6341 (1990). | en_US |
dc.identifier.citedreference | B. M. Toselli, J. D. Brenner, M. L. Yerram, W. E. Chin, K. D. King, and J. R. Barker, J. Chem. Phys. 95, 176 (1991). | en_US |
dc.identifier.citedreference | J. R. Barker, M. J. Rossi, and J. R. Pladziewicz, Chem. Phys. Lett. 90, 99 (1982). | en_US |
dc.identifier.citedreference | B. M. Toselli and J. R. Barker, J. Chem. Phys. 95, 8108 (1991). | en_US |
dc.identifier.citedreference | B. M. Toselli, T. L. Walunas, and J. R. Barker, J. Chem. Phys. 92, 4793 (1990). | en_US |
dc.identifier.citedreference | A. Chimbayo, B. M. Toselli, and J. R. Barker (manuscript in preparation). | en_US |
dc.identifier.citedreference | H. Hippler and J. Troe, in Bimolecular Collisions, edited by M. N. R. Ashford and J. E. Baggott (Royal Society of Chemistry, London, 1989), p. 209. | en_US |
dc.identifier.citedreference | H. Hippler, L. Lindemann, and J. Troe, J. Chem. Phys. 83, 3906 (1985); H. Hippler, B. Otto, and J. Troe, Ber. Bunsenges. Phys. Chem. 93, 428 (1989). | en_US |
dc.identifier.citedreference | H. Hippler, J. Troe, and J. Wendelken, J. Chem. Phys. 78, 6709, 6718 (1983). | en_US |
dc.identifier.citedreference | M. Heymann, H. Hippler, D. Nahr, H. J. Plach, and J. Troe, J. Phys. Chem. 92, 5507 (1988). | en_US |
dc.identifier.citedreference | J. E. Dove, H. Hippler, and J. Troe, J. Chem. Phys. 82, 1907 (1985); M. Heymann, H. Hippler, H. J. Plach, and J. Troe, 87, 3867 (1987). | en_US |
dc.identifier.citedreference | M. Damm, F. Deckert, H. Hippler, and J. Troe, J. Phys. Chem. 95, 2005 (1991). | en_US |
dc.identifier.citedreference | W. Jalenak, R. E. Weston, Jr., T. J. Sears, and G. W. Flynn, J. Chem. Phys. 89, 2015 (1988). | en_US |
dc.identifier.citedreference | J. Z. Chou, S. A. Hewitt, J. F. Hershberger, B. B. Brady, G. B. Spector, L. Chia, and G. W. Flynn, J. Chem. Phys. 91, 5392 (1989); J. Z. Chou, S. A. Hewitt, J. F. Hershberger, and G. W. Flynn, 93, 8474 (1990). | en_US |
dc.identifier.citedreference | A. J. Sedlacek, R. E. Weston, and G. W. Flynn, J. Chem. Phys. 94, 6483 (1991). | en_US |
dc.identifier.citedreference | (a) D. C. Tardy and B. S. Rabinovitch, Chem. Rev. 77, 369 (1977); (b) M. Quack and J. Troe, Gas Kinetics and Energy Transfer (Chemical Society, London, 1977), Vol. 2, p.175. | en_US |
dc.identifier.citedreference | R. G. Gilbert and S. C. Smith, Theory of Unimolecular and Recombination Reactions (Blackwell Scientific, Oxford, 1990), Chap. 5. | en_US |
dc.identifier.citedreference | R. G. Gilbert, J. Chem. Phys. 80, 5501 (1984). | en_US |
dc.identifier.citedreference | K. F. Lim and R. G. Gilbert, J. Phys. Chem. 94, 72, 77 (1990). | en_US |
dc.identifier.citedreference | (a) K. F. Lim and R. G. Gilbert, J. Chem. Phys. 84, 6129 (1986); (b) K. F. Lim and R. G. Gilbert, 92, 1819 (1990). | en_US |
dc.identifier.citedreference | R. G. Gilbert and R. N. Zare, Chem. Phys. Lett. 167, 407 (1990). | en_US |
dc.identifier.citedreference | B. M. Toselli and J. R. Barker, Chem. Phys. Lett. 174, 304 (1990). | en_US |
dc.identifier.citedreference | B. J. Orr and I. W. M. Smith, J. Phys. Chem. 91, 6106 (1987). | en_US |
dc.identifier.citedreference | J. L. Knee, C. E. Ottis, and P. M. Johnson, J. Chem. Phys. 81, 4455 (1984). | en_US |
dc.identifier.citedreference | J. S. Swenton, in Isotopes in Organic Chemistry, edited by E. Buncel and C. C. Lee (Elsevier Scientific, Amsterdam, 1975), p. 241. | en_US |
dc.identifier.citedreference | T. E. Martin and A. H. Kalantar, Chem. Phys. Lett. 1, 623 (1968); P. M. Johnson and M. Studer, 18, 341 (1973). | en_US |
dc.identifier.citedreference | R. H. Page, R. H. Shen, and Y. T. Lee, J. Chem. Phys. 88, 5362 (1988); J. A. Draeger, Spectrochim. Acta 41, 607 (1985); H. D. Rudolph, H. Dreizler, A. Jauschke, and P. Wendling, Z. Naturforsch. 22, 940 (1967); N. Fuson, C. Garrigou-Lagrange, and M. L. Josien, Spectrochim. Acta 16, 106 (1960); T. Shimanouchi, Tables of Molecular Vibrational Frequencies, Vol. I, edited by NSRDS (1972); L. Goodman, A. G. Ozkabak, and S. N. Thakur, J. Phys. Chem. 95, 9044 (1991). | en_US |
dc.identifier.citedreference | G. Z. Whitten and B. S. Rabinovitch, J. Chem. Phys. 41, 1883 (1964). | en_US |
dc.identifier.citedreference | (a) W. Forst, Theory of Unimolecular Reactions (Academic, New York, 1973); (b) P. J. Robinson and K. A. Holbrook, Unimolecular Reactions (Wiley, New York, 1972), p. 137. | en_US |
dc.identifier.citedreference | T. C. Brown, K. D. King, and R. G. Gilbert, Int. J. Chem. Kinet. 20, 549 (1988). | en_US |
dc.identifier.citedreference | T. C. Brown, Ph.D. thesis, The University of Adelaide, Australia, 1988. | en_US |
dc.identifier.citedreference | J. D. Brenner and J. R. Barker, Astrophys. J. Lett. 388, L39 (1992). | en_US |
dc.identifier.citedreference | R. G. Gilbert (private communication, 1991). | en_US |
dc.identifier.citedreference | R. N. Schwartz, Z. I. Slawsky, and K. F. Herzfeld, J. Chem. Phys. 20, 1591 (1952). | en_US |
dc.identifier.citedreference | F. I. Tanczos, J. Chem. Phys. 30, 1119 (1959). | en_US |
dc.identifier.citedreference | J. T. Yardley, Introduction to Molecular Energy Transfer (Academic, New York, 1980), Chap. 4. | en_US |
dc.identifier.citedreference | (a) S. Hassoon, I. Oref, and C. Steel, J. Chem. Phys. 89, 1743 (1988); (b) I. M. Morgulis, S. S. Sapers, C. Steel, and I. Oref, 90, 923 (1989); (c) A. Pashutzki and I. Oref, J. Phys. Chem. 92, 178 (1988). | en_US |
dc.identifier.citedreference | H. G. Löhmannsröben and K. Luther, Chem. Phys. Lett. 144, 473 (1988); K. Luther and K. Reihs, Ber. Bunsenges. Phys. Chem. 92, 442 (1988); K. Luther (private communication). | en_US |
dc.identifier.citedreference | G. Lendvay and G. C. Schatz, J. Phys. Chem. 94, 8864 (1990). | en_US |
dc.owningcollname | Physics, Department of |
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