T H E
J O U R N A L
O F
PHYSICAL CHEMISTRY Registered i n U.S. Patent Office 0 Copyright, 1976, by the American Chemical Society
VOLUME 80, NUMBER 20 SEPTEMBER 23, 1976
Michael Kasha Symposium
Electronic Processes and Energy Transfer in Organic, Inorganic, and Biological Systems FLORIDASTATEUNIVERSITY,TALLAHASSEE, FLORIDA THURSDAYJANUARY8-SATURDAYJANUARY
10,1976
Introductory Remarks G. A. Crosby Department of Chemistry, Washington State University, Pullman, Washington 99 163 Publication costs assisted by the Department of Chemistry, Washington State University
During the three decades since World War I1 the expansion of our knowledge about molecular electronic excited states has been rapid and fundamental. Increasingly powerful instrumentation and theoretical formulations pushed the frontiers both deeper and wider, so far, in fact, that investigators in particular areas began to lose the sense of fundamental unity relating their studies to those of others. Thus, a conference emphasizing current research on molecular electronic processes to illuminate their prominent role in organic, inorganic, and biological investigations was deemed desirable. A primary objective of the meeting was to bring together a group of active scientists, all trained in the field of molecular spectroscopy, who were applying their methods to areas of relevance to molecular energy transfer problems involving organic, inorganic, and biological systems. No attempt was made to cover all the areas related to electronic processes. Indeed, this would have been a futile exercise. A concerted effort was made, however, to underscore the unity of the current research activities in spite of their obvious diversity.
While selecting a tentative roster of participants, the initial organizers recognized the influence of Michael Kasha, both through his own research and especially through the large number of active scientists who have sojourned in his laboratory, either as students, postdoctoral fellows, or visitors. The
recognition of Professor Kasha’s influence supplied the underlying harmony sought by the Committee and, incidentally, identified Tallahassee as the obvious location for the meeting. Choice of most of the plenary speakers from former Kasha associates supplied the themes and the emphases of the Conference and, at the same time, guaranteed a rare camaraderie. Contributed papers spanning all the principal areas of the Conference added a rich diversity of ideas and discussion to the meeting. For partial support of the Kasha Symposium the organizers are grateful to the National Science Foundation, the Energy Research and Development Administration, the Division of Arts and Sciences of Florida State University, the DuPont Science and Engineering Fund of the Florida State University Department of Chemistry, and Control Data Corporation. We are grateful to the Session Chairmen for their help with the program. A special note of thanks is due to Jane Crosby not only for typing the recorded discussion and contributing to its editing but for her constant help throughout the planning and staging of the Conference. A warm note of thanks also goes to Barbara Rhodes for arranging the banquet.
Organizing Committee: G. A. Crosby (Washington State University), M. A. El-Sayed (University of California, Los Angeles), W. C. Rhodes and J. Saltiel (Florida State University). 2143
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List of Participants and Affiliation
Adar, Fran, Department of Biochemistry and Biophysics, University of Pennsylvania, Philadelphia, Pa. Akins, Daniel, Department of Chemistry, University of South Florida, Tampa, Fla. Barrett, T. W., Department of Physiology and Biophysics, University of Tennessee, Memphis, Tenn. Bass, George, Department of Molecular Biology, University of Tennessee, Memphis, Tenn. Baum, J. Clayton, Department of Chemistry, Florida State University, Tallahassee, Fla. Becker, R. S., Department of Chemistry, University of Houston, Houston, Tex. Bernstein, Elliot R., Department of Chemistry, Colorado State University, Fort Collins, Colo. Brabham, Dale E., Department of Biochemistry, University of Georgia, Athens, Ga. Callis, Patrik R., Department of Chemistry, Montana State University, Bozeman, Mont. Campion, Alan, Department of Chemistry, University of California, Los Angeles, Calif. Canters, G. W., Department of Chemistry, University of Leiden, The Netherlands. Careri, Giorgio, Laboratori Snam-Progetti, University of Rome, Monterotondo, Rome, Italy. Christensen, Ronald L., Department of Chemistry, Wesleyan University, Middletown, Conn. Clarke, Richard H., Department of Chemistry, Boston University, Boston, Mass. Clifford, James, Department of Chemistry, University of Puget Sound, Tacoma, Wash. Colson, Steven D., Sterling Chemistry Laboratory, Yale University, New Haven, Conn. Cormier, Milton J., Department of Biochemistry, University of Georgia, Athens, Ga. Crosby, Glenn, Department of Chemistry, Washington State University, Pullman, Wash. Daniels, Malcolm, Department of Chemistry, Oregon State University, Corvallis, Oreg. Das, Paritosh Kumar, Department of Chemistry, University of Houston, Houston, Tex. Dellinger, Barry, Department of Chemistry, Florida State University, Tallahassee, Fla. Demas, James, Department of Chemistry, University of Virginia, Charlottesville, Va. Doetschman, David, Department of Chemistry, State University of New York, Binghamton, N.Y. El-Bayoumi, Ashraf, Biophysics Department, Michigan State University, East Lansing, Mich. El-Sayed, Mostafa, Department of Chemistry, University of California, Los Angeles, Calif. Frank, Harry, Department of Chemistry, Boston University, Boston, Mass. Freed, Simon, Department of Chemistry, Brookhaven National Laboratory, Upton, Long Island, N.Y. Gaffron, Hans, Departments of Biology and Chemistry, Florida State University, Tallahassee, Fla. (Retired). Geacintov, Nicholas E., Chemistry Department, New York University, New York, N.Y. Giacometti, G., Instituto di Chimica Fisica, Universita di Padova, Padova, Italy. Gillispie, Gregory D., Department of Chemistry, Wayne State University, Detroit, Mich. The Journal of Physical Chemistry, Vol. 80, No. 20, 1976
Goodman, Lionel, School of Chemistry, Rutgers University, New Brunswick, N.J. Gouterman, Martin, Department of Chemistry, University of Washington, Seattle, Wash. Green, William H., Mahoney, Hadlow, Chambers & Adams, Attorneys, Tallahassee, Fla. Hameka, H. F., Department of Chemistry, University of Pennsylvania, Philadelphia, Pa. Hempel, Judith C., Department of Chemistry, Wake Forest University, Winston-Salem, N.C. Henry, Bryan R., Department of Chemistry, University of Manitoba, Winnipeg, Manitoba, Canada. Hipps, K. W., Department of Chemistry, University of Michigan, Ann Arbor, Mich. Hochstrasser, Robin M., Department of Chemistry, University of Pennsylvania, Philadelphia, Pa. Hug, Gordon, Department of Chemistry, University of Houston, Houston, Tex. Kasha, Michael, Department of Chemistry and Institute of Molecular Biophysics, Florida State University, Tallahassee, Fla. Kawaoka, Kenji, Chemistry Division, Eastman Kodak Company, Rochester, N.YI Khalil, Omar, School of Chemistry, Rutgers University, New Brunswick, N.J. Khan, Ahsan U., Department of Chemistry, Michigan State University, East Lansing, Mich. Koester, Vaughn, Department of Chemistry, Purdue University, West Lafayette, Ind. Kopelman, Raoul, Department of Chemistry, University of Michigan, Ann Arbor, Mich. Lim, Edward C., Department of Chemistry, Wayne State University, Detroit, Mich. Linder, Bruno, Department of Chemistry, Florida State University, Tallahassee, Fla. Longworth, J. W., Biology Division, Oak Ridge National Laboratory, Oak Ridge, Tenn. Mauzerall, David, Rockefeller University, New York, N.Y. McClure, D. S., Department of Chemistry, Princeton University, Princeton, N.J. McGlynn, Sean, Department of Chemistry, Louisiana State University, Baton Rouge, La. Moomaw, William R., Department of Chemistry, Williams College, Williamstown, Mass. Morgan, James, Chemistry Department, Oregon State University, Corvallis, Oreg. Muenter, Annabel A., Emulsion Research Laboratory, Eastman Kodak Company, Rochester, N.Y. Mulliken, Robert S., Department of Chemistry, University of Chicago, Chicago, Ill. Nicol, Malcolm F., Department of Chemistry, University of California, Los Angeles, Calif. Noyes, W. Albert, Department of Chemistry, The University of Texas at Austin, Austin, Tex. Parmenter, Charles, Department of Chemistry, Indiana University, Bloomington, Ind. Quagliano, James V., Department of Chemistry, Auburn University, Auburn, Ala. Rahn, Ronald, Biology Division, Oak Ridge National Laboratory, Oak Ridge, Tenn. Rawls, H. Ralph, Gulf South Research Institute, New Orleans, La.
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Rhodes, William, Department of Chemistry, Florida State University, Tallahassee, Fla. Ross, Ian G., Department of Chemistry, Australian National University, Canberra, Australia. Sager, W. F., Chemistry Department, University of Illinois at Chicago Circle, Chicago, Ill. Saltiel, Jack, Department of Chemistry, Florida State University, Tallahassee, Fla. Schatz, Paul N., Department of Chemistry, University of Virginia, Charlottesville, Va. Seliger, Howard, McCollum-Pratt Institute and Department of Biology, Johns Hopkins University, Baltimore, Md. Seybold, Paul, Chemistry Department, Wright State University, Dayton, Ohio. Simpson, W. T., Department of Chemistry, University of Oregon, Eugene, Oreg. Stevens, Brian, Department of Chemistry, University of South Florida, Tampa, Fla. Strickler, Stewart, Department of Chemistry, University of Colorado, Boulder, Colo. Stwalley, William C., Chemistry Division, National Science Foundation, Washington, D.C.
Takemura, Takeshi, Department of Chemistry, University of Houston, Houston, Tex. Tollin, Gordon, Department of Chemistry, University of Arizona, Tucson, Ariz. Vala, Martin T., Jr., Department of Chemistry, University of Florida, Gainesville, Fla. VanZee, Richard J., Department of Chemistry, Michigan State University, East Lansing, Mich. Walborsky, Harry M., Department of Chemistry, Florida State University, Tallahassee, Fla. Ward, William W., Department of Biochemistry, University of Georgia, Athens, Ga. Watson, Brian, Department of Chemistry, University of Miami, Coral Gables, Fla. Williams, Theodore P., Department of Biological Science, Florida State University, Tallahassee, Fla. Wilson, Robert W., Institute of Molecular Biology, University of Oregon, Eugene, Oreg. Windsor, Maurice, Department of Chemistry, Washington State University, Pullman, Wash. Yang, N. C., Department of Chemistry, University of Chicago, Chicago, Ill.
Participating FSU Graduate Students Katherine Bisset Craig Brown Ron Cable Scott Chambers
David Chang Dennis Cravens Steve Finson Gama1 Khalil
David Lorenz Claude Needham Steve Redmann
Pradeep Sengupta William Smothers Joseph Zupancic
The Journal of Physical Chemistry, Vol. 80, No. 20, 1976
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MICHAEL KASHA SYMPOSIUM ON ENERGY TRANSFER IN ORGANIC, INORGANIC, AND BIOLOGICAL SYSTEMS (Papers as presented at the sessions.)
SESSION I: Plenary Lectures Session Chairman: Ian Ross, Australian National University
Stewart Strickler, University of Colorado Use of True Born-Oppenheimer Wavefunctions in the Treatment of Vibronic Effects and Born-Oppenheimer Breakdown Robin Hochstrasser, University of Pennsylvania Studies of Fast Processes in the Condensed Phase Bryan Henry, University of Manitoba A General Local Mode Theory for the Description of Highly Vibrationally Excited Molecules with Applications to the Description of Polyatomic Overtone Spectra
* Lionel Goodman, Rutgers University Vibrational Electronic Interactions between Aromatic Carbonyl Triplet States
SESSION 11: Contributed Lectures Session Chairman: C. Parmenter, Indiana University
B. Stevens and J. A. Ors, University of South Florida Excitation Energy Fission in Solution
* Gregory D. Gillispie and E. C. Lim, Wayne State University Small Molecule Photochemistry. I. Theory and Application to Formaldehyde
David C. Doetschman, State University of New York a t Binghamton Relaxation Processes in Photochemical Reactions: An Electron Spin Echo Study of Chemically Induced Spin Orientation Omar S. Khalil and Lionel Goodman, Rutgers University Vibronic Interactions in the Lowest Triplet State of 9,lO-Anthraquinone
* G. Hug and R. S. Becker, University of Houston Solvent and Temperature Effects on Natural Radiative Lifetimes of Some Substituted Polyenes
Session Chairman: E. Bernstein, Colorado State University
Annabel A. Muenter, Eastman Kodak Research Laboratories Fluorescence Lifetimes and Sensitization Rate Constants for Dyes Adsorbed to Silver Halide Microcrystals Fran Adar, University of Pennsylvania, and Martin Gouterman, University of Washington Fluorescence, Resonance Raman, and Radiationless Decay in Several Hemoproteins Raoul Kopelman, University of Michigan Exciton Percolation in Mixed Molecular Crystals and Aggregates: From Naphthalene to Photosynthesis
* S. D. Colson, F. B. Tudron, R. E. Turner, and V. Vaida, Yale University On the Triplet Energy Transfer Mechanism in Isotopic Mixed Molecular Crystals
Ronald L. Christensen and Bryan E. Kohler, Wesleyan University High Resolution Optical Spectroscopy of Polyenes Related to the Visual Chromophore Malcolm F. Nicol, University of California-Los Angeles Pressure Tuning of Fluorescence Spectra Due to Deep Traps in Anthracene and Naphthalene Crystals The Journal of Physical Chemistry, Voi. 80, No. 20, 1976
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SESSION 111: Plenary Lectures Session Chairman: D. S. McClure, Princeton University
* Mostafa El-Sayed, University of California-Los
Angeles
Triplet Spin Labels and Molecular Dynamics
Glenn Crosby, Washington State University Excited States of Mixed Ligand Chelates of Ruthenium(I1) and Rhodium(II1)
* Sean McGlynn, Louisiana State University The Color of Inorganic Ions
Ahsan Khan, Michigan State University Singlet Molecular Oxygen: A New Kind of Oxygen
SESSION IV: Contributed Lectures Session Chairman: M Gouterman, University of Washington * A. Campion and M. A. El-Sayed, University of California-Los Angeles The Mechanism of the SI w> TI Intersystem Crossing in Duraldehyde by Zeeman-PMDR Techniques
* E. R. Bernstein, G . R. Meredith, and J. D. Webb, Colorado State University Jahn-Teller Effect and Vibronic Coupling in Octahedral Molecules-ReF6 and IrF6
Harry G . Brittain, F. S. Richardson, J. P. Jasinski, and P. N. Schatz, University of Virginia Magnetic Circularly Polarized Emission from Crystalline Cs2ZrC16:Re4+
K. W. Hipps, G . A. Merrell, and G . A. Crosby, Washington State University Geometrical Distortion of the Excited States of d6 Transition Metal Complexes: Systems of 0 and Dd Symmetry
Richard J. VanZee and Ahsan U. Khan, Michigan State University The Phosphorescence of Phosphorus
Session Chairman: H. F. Hameka, University of Pennsylvania
William R. Moomaw, Williams College Luminescence Studies of Proton Transfer in the Excited Electronic States of Hydrogen Bonded Quinoline and Isoquinoline
* D. L. Akins, University of South Florida Energy Transfer and Electron Transfer Rate Constants in Electrochemiluminescent (ECL) Systems
D. G . Taylor, R. P. McBride, E. W. Harris, and J. N. Demas, University of Virginia New Tools in Photochemistry and Photophysics
* T . W . Barrett, University of Tennessee Parametric Excitation as the Means of Energy Transfer in Quantal Systems With Reference to Carcinogens
G. W. Canters, G . Jansen, M. Noort, Gorlaeus Laboratories, and J. H. van der Waals, Huygens Laboratory, Rijksuniversiteit High Resolution Zeeman Experiments on Singlet, Triplet, and Quartet States of Metalloporphines SESSION V: Plenary Lectures Session Chairman: W. Simpson, University of Oregon
Ashraf El-Bayoumi, Michigan State University Relaxation Processes in Excited Molecular Systems. Some Biological Applications Ralph Becker, University of Houston
The Spectroscopy and Photochemistry of Model Visual Pigments
Gordon Tollin, University of Arizona Model Systems for Photosynthetic Energy Conversion
* Maurice Windsor, Washington State University Picosecond Flash Photolysis Studies of Dyes, Biological Pigments, and Photosynthetic Systems The Journal of Physical Chemistry,, Vol. 80, No. 20, 1976
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SESSION VI: Contributed Lectures Session Chairman: Simon Freed, Brookhaven National Laboratory
* Robert W. Wilson, University of Oregon, J. P. Morgan, Oregon State University, and Patrik R. Callis, Montana State University Anomalous Fluorescence Excitation Spectra in the DNA Bases: Are We Asking Too Much of Vavilov’s Law?
James Morgan and Malcolm Daniels, Oregon State University Polarization Studies of the Excited States of the Nucleic Acid Bases at Room Temperature Robert W. Wilson, University of Oregon, and Patrik R. Callis, Montana State University Polarized Fluorescence of the Dinucleotides William W. Ward and Milton J. Cormier, University of Georgia In Vitro Energy Transfer in Renilla Bioluminescence Dale E. Brabham and John Lee, University of Georgia Excited State Interactions of a-Tocopherol and Molecular Oxygen Howard Seliger, Johns Hopkins University Chemiluminescence from Liver Microsomes During Hydroxylation of Carcinogens D. Mauzerall, Rockefeller University Multiple Excitations in Photosynthetic Systems Vaughn Koester and Francis K. Fong, Purdue University Physicochemical Properties of tlie 700 nm Absorbing Chlorophyll a.HzO Dimer * Papers marked with an asterisk were presented at the Symposium but, for various reasons, are not included in this symposium issue, or are included in abstract or modified form.
The Journal of Physical Chemistry, Vol. 80, No. 20, 1976
