کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5375903 | 1504311 | 2008 | 10 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Time-resolved infrared spectroscopy of the lowest triplet state of thymine and thymidine
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موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی تئوریک و عملی
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چکیده انگلیسی
Vibrational spectra of the lowest energy triplet states of thymine and its 2â²-deoxyribonucleoside, thymidine, are reported for the first time. Time-resolved infrared (TRIR) difference spectra were recorded over seven decades of time from 300 fs to 3 μs using femtosecond and nanosecond pump-probe techniques. The carbonyl stretch bands in the triplet state are seen at 1603 and â¼1700 cmâ1 in room-temperature acetonitrile-d3 solution. These bands and additional ones observed between 1300 and 1450 cmâ1 are quenched by dissolved oxygen on a nanosecond time scale. Density-functional calculations accurately predict the difference spectrum between triplet and singlet IR absorption cross sections, confirming the peak assignments and elucidating the nature of the vibrational modes. In the triplet state, the C4O carbonyl exhibits substantial single-bond character, explaining the large (â¼70 cmâ1) red shift in this vibration, relative to the singlet ground state. Femtosecond TRIR measurements unambiguously demonstrate that the triplet state is fully formed within the first 10 ps after excitation, ruling out a relaxed 1nÏâ state as the triplet precursor.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Chemical Physics - Volume 347, Issues 1â3, 23 May 2008, Pages 383-392
Journal: Chemical Physics - Volume 347, Issues 1â3, 23 May 2008, Pages 383-392
نویسندگان
Patrick M. Hare, Chris T. Middleton, Kristin I. Mertel, John M. Herbert, Bern Kohler,