The threshold photoelectron spectrum (TPES) of HOBr has been obtained in the wavelength regions corresponding to the first and second ionization bands. The adiabatic ionization potential (IP) is 10.642±0.005 eV; the O–Br stretching frequency in this X2A″ state is found to be 730±20 cm−1. The adiabatic IP for the first excited state (A2A′) of HOBr+ is 11.448±0.005 eV. The latter value confirms an earlier, tentative conclusion based on the interpretation of autoionizing structure in the photoionization mass spectrum (PIMS). There is a slight difference in the TPES and PIMS values of the first adiabatic IP, whose origin is still somewhat ambiguous.

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