Publication Date:
2010-07-03
Description:
Since the discovery of the hydrated electron more than 40 years ago, a general consensus has emerged that the hydrated electron occupies a quasispherical cavity in liquid water. We simulated the electronic structure and dynamics of the hydrated electron using a rigorously derived pseudopotential to treat the electron-water interaction, which incorporates attractive oxygen and repulsive hydrogen features that have not been included in previous pseudopotentials. What emerged was a hydrated electron that did not reside in a cavity but instead occupied a approximately 1-nanometer-diameter region of enhanced water density. Both the calculated ground-state absorption spectrum and the excited-state spectral dynamics after simulated photoexcitation of this noncavity hydrated electron showed excellent agreement with experiment. The relaxation pathway involves a rapid internal conversion followed by slow ground-state cooling, the opposite of the mechanism implicated by simulations in which the hydrated electron occupies a cavity.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Larsen, Ross E -- Glover, William J -- Schwartz, Benjamin J -- New York, N.Y. -- Science. 2010 Jul 2;329(5987):65-9. doi: 10.1126/science.1189588.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569, USA. Ross.Larsen@nrel.gov〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/20595609" target="_blank"〉PubMed〈/a〉
Print ISSN:
0036-8075
Electronic ISSN:
1095-9203
Topics:
Biology
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Chemistry and Pharmacology
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Computer Science
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Medicine
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Natural Sciences in General
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Physics
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