The Phosphorescence Processes in Pyrimidine and 2-Chloropymidine
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The phosphorescence spectra of pyrimidine and 2-chloropyrimidine have been observed at 4.2°K. A detailed vibrational analysis of the pyrimidine spectrum suggests that the emission arises from two components of the emitting triplet state. The phosphorescence lifetimes of pyrimidine and 2-chloropyrimidine have been measured for the 0-0 band and the strongest "vibronic band" (the phosphorescence maximum), which involves various modes of vibrations, at different temperatures between 77 and 1.5°K. The decay curve observed for the 0-0 band has been resolved into two exponential components, and that for the vibronic band, into three exponential components, where the third component was extremely weak in intensity at a very low temperature. From the comparison of the observed and calculated lifetimes of the individual phosphorescence components and their relative intensities, it was deduced that: (1) the 0-0 band involves emissions arising from the <I>B</I><SUB>2</SUB> and <I>A</I><SUB>1</SUB> components of the <SUP>3</SUP><I>B</I><SUB>1</SUB>(<I>n</I>,π<SUP>*</SUP>) state, while the vibronic band involves an additional, third emission which very likely arises from the <I>A</I><SUB>2</SUB> component; (2) the <SUP>1</SUP><I>A</I><SUB>2</SUB>(<I>n</I>,π<SUP>*</SUP>) state is located below the <SUP>1</SUP><I>B</I><SUB>1</SUB>(<I>n</I>,π<SUP>*</SUP>) state; (3) the <SUP>3</SUP><I>A</I><SUB>1</SUB>(π,π<SUP>*</SUP>) state is located below the <SUP>1</SUP><I>A</I><SUB>2</SUB>(<I>n</I>,π<SUP>*</SUP>) state, and (4) the major intersystem crossing takes place from both the <SUP>1</SUP><I>A</I><SUB>2</SUB>(<I>n</I>,π<SUP>*</SUP>) and <SUP>1</SUP><I>B</I><SUB>1</SUB>(<I>n</I>,π<SUP>*</SUP>) states to the <SUP>3</SUP><I>A</I><SUB>1</SUB>(π,π<SUP>*</SUP>) state in pyrimidine and 2-chloropyrimidine.
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- The Phosphorescence Processes in Pyrimidine and 2-Chloropymidine