Abstract
Analysis of the steady-state absorption/fluorescence spectra of several laser dyes in room temperature solution suggests that the fluorescing molecules, if initially formed in a vibrationally excited state, lose their excess energy surprisingly slowly, remaining significantly warm on a nanosecond time scale. A similar analysis of the steady-state absorption/fluorescence spectra of GaAs confirms that in this case the carriers are fully thermalized, possessing no excess energy when they recombine on a microsecond time scale. A classical model which accounts qualitatively for slow molecular cooling is presented. We conclude that rapid molecular photoconversion processes are likely to involve incompletely cooled (thermalized) excited states.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
J. R. Bolton and M. D. Archer, J. Phys. Chem., 95, 8453 (1991).
J. Shah, Hot Carriers in Semiconductor Nanostructures, Academic, New York, 1992.
Y. Rosenwaks, M.C. Hanna, D.H. Levi, D.M. Szmyd, R.K. Ahrenkiel, and A.J. Nozik, Phys. Rev. B, 48, 14675 (1993) and references therein.
K. W. Barnham, J. M. Barnes, B. Brown, J. P. Connolly, G. Haarpaintner, J. A. Nelson, M. Paxman, C. Button, and J. S. Roberts, Proc. 11th EC Photovoltaic Specialists Conf., Montreux, 1992.
C. A. Parsons, M. W. Peterson, B. R. Thacker, J. A. Turner, and A. J. Nozik, J. Phys. Chem., 94, 3381 (1990).
A. J. Nozik, Y. Rosenwaks, B. R. Thacker, M. C. Hanna, C. Curtis, J. Sprague, and J. Turner, Proc. 17th DOE Solar Photochemistry Research Conf., June 1993, p. 97, available from the National Technical Information Service, U.S. Department of Commerce, 5285 Port Royal Road, Springfield, VA, 22161.
W. S. Pelouch, R. J. Ellingson, P. E. Powers, C. L. Tang, D. M. Szmyd, and A. J. Nozik, Phys. Rev.B, 45, 1450 (1992).
V. B. Campos, S. Das Sarma, and M. A. Stroscio, Phys. Rev. B, 46, 3849 (1992).
T. Elsaesser and W. Kaiser, Ann. Rev. Phys. Chem., 42, 83 (1991).
M. Maroncelli, Proc. 17th DOE Solar Photochemistry Research Conf., June 1993, p. 5, available from the National Technical Information Service, U.S. Department of Commerce, 5285 Port Royal Road, Springfield, VA, 22161.
U. Sukowski, A. Seilmeier, and T. Elsaesser, J. Chem. Phys., 93, 4094 (1990).
W. van Roosbroeck and W. Shockley, Phys. Rev., 94, 1558 (1954).
Th. Förster, Fluoreszenz Organischer Verbindungen, Vandenhoeck und Ruprecht, Göttingen, 1951, p.158.
S. J. Strickler and R. A. Berg, J. Chem. Phys., 37, 814 (1962).
J. Hevesi, I. Ketskemety, and L. Kozma, Acta Phys. Chem. Szeged, 11, 81 (1965).
A. Erdélyi, W. Magnus, F. Oberhettinger and F. A. Tricomi, Tables of Integral Transforms, Vol. 1, McGraw-Hill, New York, 1954, p. 246.
J. Mathews and R. L. Walker, Methods of Mathematical Physics, Benjamin, Menlo Park, CA, 1965.
Author information
Authors and Affiliations
Additional information
An erratum to this article is available at http://dx.doi.org/10.1163/156856795X00189.
Rights and permissions
About this article
Cite this article
Archer, M.D., Bolton, J.R. & Siklos, S.S.T. Thermalization of photoexcited molecules in solution. Res Chem Intermed 20, 909–926 (1994). https://doi.org/10.1163/156856794X00289
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1163/156856794X00289