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Assessing solvent effects on the singlet excited state lifetime of uracil derivatives: A femtosecond fluorescence upconversion study in alcohols and D2O (34 views)

Gustavsson T, Bányász A, Sarkar N, Markovitsi D, Improta R

Chem Phys (ISSN: 0301-0104), 2008 Jun 23; 350(1-3): 186-192.

Abstract
The excited state lifetimes of uracil, thymine and 5-fluorouracil have been measured using femtosecond UV fluorescence upconversion in various protic and aprotic polar solvents. The fastest decays are observed in acetonitrile and the slowest in aqueous solution while those observed in alcohols are intermediate. No direct correlation with macroscopic solvent parameters such as polarity or viscosity is found, but hydrogen bonding is one key factor affecting the fluorescence decay. It is proposed that the solvent modulates the relative energy of two close-lying electronically excited states, the bright ππ* and the dark nπ* states. This relative energy gap controls the non-radiative relaxation of the ππ* state through a conical intersection close to the Franck-Condon region competing with the ultrafast internal conversion to the ground state. In addition, an inverse isotope effect is observed in D2O where the decays are faster than in H2O. © 2008 Elsevier B.V. All rights reserved.

Affiliations ▼
*** IBB - CNR Affiliation

Laboratoire Francis Perrin, CEA/DSM/DRECAM/SPAM - CNRS URA 2453, CEA/Saclay, F-91191 Gif-sur-Yvette, France

Department of Chemistry, Indian Institute of Technology, Kharagpur, 721 302 WB, India

Dipartimento di Chimica, Universita Federico II, Complesso Universitario Monte S. Angelo, Via Cintia, I-80126 Napoli, Italy

Istituto Biostrutture e Bioimmagini, CNR, V. Mezzocannone 6, 80134 Napoli, Italy

Details ▼
Impact factor: 2.028, 5-year impact factor: 1.857

Paper type: Journal Article,

Keywords: Conical Intersection, Dna, Excited States, Femtosecond, Fluorescence Upconversion, Nucleobases, Pyrimidines, Solvent Effect, Thymine, Uracil,

Url: http://www.scopus.com/inward/record.url?eid=2-s2.0-44749089311&partnerID=40&md5=e8a3626fabbe6f8fe26262b084a8f751

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2 Records (2 excluding Abstracts and Conferences).
Total impact factor: 6.915 (6.915 excluding Abstracts and Conferences).
Total 5-year impact factor: 7.276 (7.276 excluding Abstracts and Conferences).



Your bibliography query: (([btitle, keywords, abstract] CONICAL AND [btitle, keywords, abstract] INTERSECTION AND [btitle, keywords, abstract] EXCITED AND [btitle, keywords, abstract] STATES AND [btitle, keywords, abstract] FEMTOSECOND AND [btitle, keywords, abstract] FLUORESCENCE AND [btitle, keywords, abstract] UPCONVERSION)) AND NOT [id] = 48598



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