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Unexpected simplicity in the S1–S0 dispersed fluorescence spectra of 13C2H2

We have recorded dispersed fluorescence (DF) spectra (18 cm−1 resolution) from the JKaKc=110 rotational level of six vibrational levels in the S1 (A 1Au) state of 13C2H2. Improvements in our methods of recording and calibrating DF spectra, that have enhanced the quality of our data sets, are briefly discussed. More than 50 fractionated bright state patterns associated with approximately conserved polyad quantum numbers have been extracted from our DF data sets using a spectroscopic pattern recognition technique, extended cross correlation. These polyads extend to internal energies as high as 20 000 cm−1 above the zero-point vibrational level. The polyad fractionation patterns observed at high energy are surprisingly simple relative to the corresponding patterns of 12C2H2. Comparison between the DF spectra of 13C2H2 and 12C2H2 reveals slower intramolecular vibration redistribution in 13C2H2, particularly with nonzero quanta of CC stretch excitation. More than 15 patterns were extracted above the energy at ...