S(0) internal conversion processes. The possibility of dramatic deviations from standard energy gap law behavior is predicted. We conclude that controlling molecular conformations by rigid environments can have a substantial impact on photophysical and (bio)chemical processes." />
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Fidder H, Rini M, Nibbering ET. The role of large conformational changes in efficient ultrafast internal conversion: deviations from the energy gap law. J Am Chem Soc. 2004;126(12):3789-94doi: 10.1021/ja038741y.
Fidder, H., Rini, M., & Nibbering, E. T. (2004). The role of large conformational changes in efficient ultrafast internal conversion: deviations from the energy gap law. Journal of the American Chemical Society, 126(12), 3789-94. https://doi.org/10.1021/ja038741y
Fidder, Henk, et al. "The role of large conformational changes in efficient ultrafast internal conversion: deviations from the energy gap law." Journal of the American Chemical Society vol. 126,12 (2004): 3789-94. doi: https://doi.org/10.1021/ja038741y
Fidder H, Rini M, Nibbering ET. The role of large conformational changes in efficient ultrafast internal conversion: deviations from the energy gap law. J Am Chem Soc. 2004 Mar 31;126(12):3789-94. doi: 10.1021/ja038741y. PMID: 15038732.
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J Am Chem Soc. 2004 Mar 31;126(12):3789-94. doi: 10.1021/ja038741y.

The role of large conformational changes in efficient ultrafast internal conversion: deviations from the energy gap law.

Journal of the American Chemical Society

Henk Fidder, Matteo Rini, Erik T J Nibbering

Affiliations

  1. Department of Physical Chemistry, Uppsala University, Sweden. [email protected]

PMID: 15038732 DOI: 10.1021/ja038741y

Abstract

Conversion of electronic excitation energy into vibrational energy was investigated for photochromic spiropyran molecules, using femtosecond UV-mid-IR pump-probe spectroscopy. We observe a weaker energy gap dependence than demanded by the "energy gap law". We demonstrate that large conformational changes accompanying the optical excitation can explain the observed time scale and energy gap dependence of ultrafast S(1) --> S(0) internal conversion processes. The possibility of dramatic deviations from standard energy gap law behavior is predicted. We conclude that controlling molecular conformations by rigid environments can have a substantial impact on photophysical and (bio)chemical processes.

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