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Science 31 October 1997:
Vol. 278. no. 5339, p. 777
DOI: 10.1126/science.278.5339.777l
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Although strongly exothermic electron transfer reactions initiated by photoexcitation can be understood relatively well with existing theories, rate constants for reactions that have low exothermicity and that occur in the dark have been difficult to reproduce within these theoretical frameworks, even when tunneling is invoked to achieve better agreement between experiment and theory. Nelsen et al. show that by making a relatively small change to the adiabatic energy surfaces, the intramolecular energy transfer rate constants can be calculated accurately for a range of organic compounds without explicitly invoking tunneling terms

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Science. ISSN 0036-8075 (print), 1095-9203 (online)