Electronic relaxation processes from single vibronic levels in the S1(n,.PI.*) state of pyridine vapor.
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概要
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The rate constants of radiative decay (<I>k</I><SUB>F</SUB>), internal conversion (<I>k</I><SUB>IC</SUB>), and intersystem crossing (<I>k</I><SUB>ISC</SUB>) for single vibronic levels in the S<SUB>1</SUB>(n, π<SUP>*</SUP>) state of pyridine-<I>d</I><SUB>0</SUB> and -<I>d</I><SUB>5</SUB> vapors have been determined from measured fluorescence quantum yields (Φ<SUB>F</SUB>), intersystem crossing quantum yields (Φ<SUB>ICS</SUB>), and picosecond fluorescence lifetimes. The Φ<SUB>ISC</SUB> values are fairly constant in the region of lower excess vibrational energy (<1000 cm<SUP>−1</SUP>), while the Φ<SUB>F</SUB> values are particularly large for vibronic levels involving non-totally symmetric vibrations, ν<SUB>16b</SUB> and ν<SUB>10a</SUB>. The latter observation is attributed to both an increase of <I>k</I><SUB>F</SUB> and a decrease of <I>k</I><SUB>IC</SUB> and <I>k</I><SUB>ISC</SUB> (relative to the zero-point level) for the ν<SUB>16b</SUB> levels (16b<SUP>2</SUP> and l6b<SUP>2</SUP>6a<SUP>1</SUP>), and to an increase of <I>k</I><SUB>F</SUB> for the ν<SUB>10a</SUB> levels. The relative values of <I>k</I><SUB>F</SUB> are discussed using the Herzberg-Teller theory of vibronic coupling. The values of <I>k</I><SUB>F</SUB> for 16b<SUP>1</SUP> and 16b<SUP>2</SUP> are significantly larger than that for the zero-point level, though no absorption band corresponding to 16b<SUB>0</SUB><SUP>1</SUP> can be observed. In both pyridine-<I>d</I><SUB>0</SUB> and -<I>d</I><SUB>5</SUB>, the value of <I>k</I><SUB>IC</SUB> is as large as 1.7×10<SUP>10</SUP>s<SUP>−1</SUP> even for the zero-point level, which is more than twice the <I>k</I><SUB>ISC</SUB> value for the same level.
- 公益社団法人 日本化学会の論文
著者
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Baba Hiroaki
Division of Chemistry, Research Institute of Applied Electricity, Hokkaido University
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Fujita Masahisa
Division of Chemistry, Research Institute of Applied Electricity, Hokkaido University
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Yamazaki Iwao
Institute for Molecular Science
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Sushida Kazuyoshi
Division of Chemistry, Research Institute of Applied Electricity, Hokkaido University
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