Abstract
The C∼2B3u←X∼2B2g electronic absorption of butatriene cation (BT+) has been observed in a 6K neon matrix. The origin band lies at 511.9nm. The electronic transition assignment is based on comparison with the photoelectron spectrum of butatriene and the vibrational frequencies of BT+ calculated with the CASPT2 (5,6) method. Three vibrational modes of energy 207, 511 and 813cm−1, with their overtones and combinations, are active in the C∼2B3u state of BT+. It is shown that the emission observed from a glow discharge of 2-butyne at 491nm and attributed to the origin band of this electronic transition [1] of BT+ is due to another species, because the difference of 850cm−1 to the absorption spectrum is too large. No fluorescence of BT+ was detected in the matrix and it is expected that the C∼2B3u electronic state relaxes non-radiatively on a fs time scale.
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