JCP Nameplate
  • Volume/Page
  • Keyword
  • DOI
  • Citation
  • Advanced
   
 
 
 

You Tube Flickr Twitter UniPHY Group iResearch App Facebook

Journal of Chemical Physics / Volume 129 / Issue 1 / ARTICLES / Gas Phase Dynamics and Structure: Spectroscopy, Molecular Interactions, Scattering, and Photochemistry

J. Chem. Phys. 129, 014303 (2008); doi:10.1063/1.2943668 (11 pages)

Energy-dependent dynamics of large-ΔE collisions: Highly vibrationally excited azulene (E = 20 390 and 38 580 cm−1) with CO2

Liwei Yuan, Juan Du, and Amy S. Mullin

Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA

View MapView Map

(Received 6 November 2007; accepted 20 May 2008; published online 2 July 2008)

We report the energy dependence of strong collisions of CO2 with highly vibrationally excited azulene for two initial energies, E = 20 390 and 38 580 cm−1. These studies show that both the distribution of transferred energy and the energy transfer rates are sensitive to the azulene energy. Highly excited azulene was prepared in separate studies by absorption of pulsed excitation at λ = 532 or 266 nm, followed by rapid radiationless decay from S1 or S4 to vibrationally excited levels of the ground electronic state. The appearance of scattered CO2 (0000) molecules with Erot>1000 cm−1 was monitored by high-resolution transient IR absorption at λ = 4.3 μm. The average rotational and translational energies of the scattered CO2 molecules double when the azulene energy is increased by a factor of 2. The rate of energy transfer in strong collisions increases by nearly a factor of 4 when the azulene energy is doubled. The energy transfer probability distribution function for ΔE>3000 cm−1 at each initial energy is an exponential decay with curvature that correlates with the energy dependence of the state density, in excellent agreement with predictions from GRETCHEN, a model based on Fermi’s golden rule to describe collisional quenching of highly excited molecules.

© 2008 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. EXPERIMENTAL METHODS
  3. RESULTS AND DISCUSSION
    1. CO2 rotational energy gain from azulene(E)-CO2 large- ΔE collisions
    2. Translational energy release from azulene(E)-CO2 large- ΔE collisions
    3. Rates of azulene(E)-CO2 large- ΔE energy transfer
    4. P(ΔE) curves for large- ΔE collisions of azulene(E) and CO2
  4. CONCLUSION

RELATED DATABASES

To view database links for this article, you need to log in.

KEYWORDS and PACS

Keywords

carbon compounds, excited states, ground states, infrared spectra, molecule-molecule collisions, organic compounds, probability, rotational states, translational states, vibrational states

PACS

  • 34.50.Ez

    Rotational and vibrational energy transfer

  • 33.20.Ea

    Infrared spectra

  • 33.15.Mt

    Rotation, vibration, and vibration-rotation constants

ARTICLE DATA

Permalink
http://link.aip.org/link/doi/10.1063/1.2943668

PUBLICATION DATA

ISSN:

0021-9606 (print)  
1089-7690 (online)

Publisher:

$abstract.society.value is a Member of CrossRef American Institute of Physics

For access to fully linked references, you need to log in.
    J. Troe, J. Chem. Phys. 66, 4758 (1977)JCPSA6000066000011004758000001.

    A. S. Mullin, C. A. Michaels, and G. W. Flynn, J. Chem. Phys. 102, 6032 (1995)JCPSA6000102000015006032000001.

    C. A. Michaels, Z. Lin, A. S. Mullin, H. C. Tapalian, and G. W. Flynn, J. Chem. Phys. 106, 7055 (1997)JCPSA6000106000017007055000001.

    E. T. Sevy, S. M. Rubin, Z. Lin, and G. W. Flynn, J. Chem. Phys. 113, 4912 (2000)JCPSA6000113000012004912000001.

    E. T. Sevy, C. A. Michaels, H. C. Tapalian, and G. W. Flynn, J. Chem. Phys. 112, 5844 (2000)JCPSA6000112000013005844000001.

    E. T. Sevy, M. A. Muyskens, S. M. Rubin, G. W. Flynn, and J. T. Muckerman, J. Chem. Phys. 112, 5829 (2000)JCPSA6000112000013005829000001.

    M. C. Wall and A. S. Mullin, J. Chem. Phys. 108, 9658 (1998)JCPSA6000108000023009658000001.

    M. C. Wall, B. A. Stewart, and A. S. Mullin, J. Chem. Phys. 108, 6185 (1998)JCPSA6000108000015006185000001.

    M. S. Elioff, M. C. Wall, A. S. Lemoff, and A. S. Mullin, J. Chem. Phys. 110, 5578 (1999)JCPSA6000110000012005578000001.

    M. C. Wall, A. E. Lemoff, and A. S. Mullin, J. Chem. Phys. 111, 7373 (1999)JCPSA6000111000016007373000001.

    J. Park, L. Shum, A. S. Lemoff, K. Werner, and A. S. Mullin, J. Chem. Phys. 117, 5221 (2002)JCPSA6000117000011005221000001.

    J. Park, L. Shum, A. S. Lemoff, K. Werner, and A. S. Mullin, J. Chem. Phys. 117, 5221 (2002)JCPSA6000117000011005221000001.

    J. A. Johnson, A. M. Duffin, B. J. Hom, K. E. Jackson, and E. T. Sevy, J. Chem. Phys. 128, 054304 (2008)JCPSA6000128000005054304000001.

    U. Hold, T. Lenzer, K. Luther, K. Reihs, and A. C. Symonds, J. Chem. Phys. 112, 4076 (2000)JCPSA6000112000009004076000001.

    T. Lenzer, K. Luther, K. Reihs, and A. C. Symonds, J. Chem. Phys. 112, 4090 (2000)JCPSA6000112000009004090000001.

    U. Hold, T. Lenzer, K. Luther, and A. C. Symonds, J. Chem. Phys. 119, 11192 (2003)JCPSA6000119000021011192000001.

    C. A. Michaels and G. W. Flynn, J. Chem. Phys. 106, 3558 (1997)JCPSA6000106000009003558000001.

    C. L. Liu, H. C. Hsu, J. J. Lyu, and C. K. Ni, J. Chem. Phys. 123, 131102 (2005)JCPSA6000123000013131102000001.

    C. L. Liu, H. C. Hsu, J. J. Lyu, and C. K. Ni, J. Chem. Phys. 125, 204309 (2006)JCPSA6000125000020204309000001.

    C. L. Liu, H. C. Hsu, J. J. Lyu, and C. K. Ni, J. Chem. Phys. 124, 054302 (2006)JCPSA6000124000005054302000001.

    G. H. Kohlmaier and B. S. Rabinovitch, J. Chem. Phys. 38, 1709 (1963)JCPSA6000038000007001709000001.

    G. H. Kohlmaier and B. S. Rabinovitch, J. Chem. Phys. 38, 1692 (1963)JCPSA6000038000007001692000001.

    J. W. Simons, B. S. Rabinovitch, and D. W. Setser, J. Chem. Phys. 41, 800 (1964)JCPSA6000041000003000800000001.

    D. C. Tardy, B. S. Rabinovitch, and C. W. Larson, J. Chem. Phys. 45, 1163 (1966)JCPSA6000045000004001163000001.

    M. Heymann, H. Hippler, and J. Troe, J. Chem. Phys. 80, 1853 (1984)JCPSA6000080000005001853000001.

    J. E. Dove, H. Hippler, and J. Troe, J. Chem. Phys. 82, 1907 (1985)JCPSA6000082000004001907000001.

    H. Hippler, L. Lindemann, and J. Troe, J. Chem. Phys. 83, 3906 (1985)JCPSA6000083000008003906000001.

    M. Heymann, H. Hippler, H. J. Plach, and J. Troe, J. Chem. Phys. 87, 3867 (1987)JCPSA6000087000007003867000001.

    M. J. Rossi, J. R. Pladziewicz, and J. R. Barker, J. Chem. Phys. 78, 6695 (1983)JCPSA6000078000011006695000001.

    J. Shi and J. R. Barker, J. Chem. Phys. 88, 6219 (1988)JCPSA6000088000010006219000001.

    B. M. Toselli and J. R. Barker, J. Chem. Phys. 97, 1809 (1992)JCPSA6000097000003001809000001.

    R. V. Serauskas and E. W. Schlag, J. Chem. Phys. 42, 3009 (1965)JCPSA6000042000009003009000001.

    W. G. Valance and E. W. Schlag, J. Chem. Phys. 45, 216 (1966)JCPSA6000045000001000216000001.

    H. Von Weyssenhoff and E. W. Schlag, J. Chem. Phys. 59, 729 (1973)JCPSA6000059000002000729000001.

    R. G. Gilbert, J. Chem. Phys. 80, 5501 (1984)JCPSA6000080000011005501000001.

    K. F. Lim and R. G. Gilbert, J. Chem. Phys. 84, 6129 (1986)JCPSA6000084000011006129000001.

    D. Nilsson and S. Nordholm, J. Chem. Phys. 119, 11212 (2003)JCPSA6000119000021011212000001.

    G. Lendvay and G. C. Schatz, J. Chem. Phys. 98, 1034 (1993)JCPSA6000098000002001034000001.

    D. L. Clarke, I. Oref, R. G. Gilbert, and K. F. Lim, J. Chem. Phys. 96, 5983 (1992)JCPSA6000096000008005983000001.

    K. F. Lim, J. Chem. Phys. 100, 7385 (1994)JCPSA6000100000010007385000001.

    V. Bernshtein and I. Oref, J. Chem. Phys. 125, 133105 (2006)JCPSA6000125000013133105000001.

    T. Lenzer, K. Luther, J. Troe, R. G. Gilbert, and K. F. Lim, J. Chem. Phys. 103, 626 (1995)JCPSA6000103000002000626000001.

    T. Lenzer and K. Luther, J. Chem. Phys. 105, 10944 (1996)JCPSA6000105000024010944000001.

    M. Damm, H. Hippler, and J. Troe, J. Chem. Phys. 88, 3564 (1988)JCPSA6000088000006003564000001.

    H. Hippler, L. Lindemann, and J. Troe, J. Chem. Phys. 83, 3906 (1985)JCPSA6000083000008003906000001.

    W. Jalenak, R. E. Weston, T. J. Sears, and G. W. Flynn, J. Chem. Phys. 83, 6049 (1985)JCPSA6000083000011006049000001.

    W. Jalenak, R. E. Weston, T. J. Sears, and G. W. Flynn, J. Chem. Phys. 89, 2015 (1988)JCPSA6000089000004002015000001.

    H. C. Hsu, C. L. Liu, J. J. Lyu, and C. K. Ni, J. Chem. Phys. 124, 134303 (2006)JCPSA6000124000013134303000001.

    M. S. Elioff, M. Fang, and A. S. Mullin, J. Chem. Phys. 115, 6990 (2001)JCPSA6000115000015006990000001.

    M. F. Lin, C. L. Huang, Y. T. Lee, and C. K. Ni, J. Chem. Phys. 119, 2032 (2003)JCPSA6000119000004002032000001.

    Y. Hirata and E. C. Lim, J. Chem. Phys. 69, 3292 (1978)JCPSA6000069000007003292000001.


For access to citing articles, you need to log in.


Figures (8) Tables (2)

Access to article objects (figures, tables, multimedia) requires a subscription; log in to view available files.
(Access to supplementary files, where available, is free for this journal.)

Access to article objects (figures, tables, multimedia) requires a subscription; log in to view available files.
(Access to supplementary files, where available, is free for this journal.)



Close

Google Calendar

ADVERTISEMENT

Your Recent History Recent History Help

Recently Viewed

  1. Energy-dependent dynamics of large-ΔE collisions: Highly vibrationally excited azulene (E = 20 390 and 38 580 cm−1) with CO2
  2. Time-dependent density functional theory investigation of the absorption, fluorescence, and phosphorescence spectra of solvated coumarins
  3. Gradient theory computation of the radius-dependent surface tension and nucleation rate for n-nonane clusters
  4. The permanent electric dipole moment of chromium monodeuteride, CrD
  5. Photonic reagent control of dynamically homologous quantum systems
Go to AIP Home
Copyright © American Institute of Physics
close