Vibronic absorption spectra of the biphenyl and biphenyl-d10 cations in solid argon

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Abstract
Matrix photoionization of biphenyl vapor during condensation at 20±2 K with excess argon produced band systems at 382.8 and 669.4 nm which are assigned to biphenyl cation owing to agreement with earlier radiolysis studies. The bands are blue shifted from photoelectron band differences which indicate structural changes between the molecule and the ionic states in the gas phase or between the gas and condensed phase ionic states. Vibrational fine structure in both absorption systems exhibits appropriate deuterium shifts and correlates with symmetric modes in the Raman spectra of C12H10 and C12D10. The sharper 382.8 nm band system reveals a 1771 cm−1 splitting of this ionic state, presumably a result of inter‐ring resonance interactions.

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