Communication: A vibrational study of propargyl cation using the vacuum ultraviolet laser velocity-map imaging...

By employing the vacuum ultraviolet (VUV) laser velocity-map imaging photoelectron (VUV-VMI-PE) method, we have obtained a vibrationally resolved photoelectron spectrum of gaseous propargyl radical [C(3)H(3)(X(2)B(1))] in the energy range of 0-4600 cm(-1) above its ionization energy. The cold C(3)H(3) radicals were produced from a supersonically cooled radical beam source based on 193 nm ArF photodissociation of C(3)H(3)Cl. The VUV-VMI-PE spectrum of C(3)H(3) thus obtained reveals a Franck-Condon factor (FCF) pattern with a highly dominant origin band along with weak vibrational progressions associated with excitations of the C-C ν(5)(+)(a(1)) and C≡C ν(3)(+)(a(1)) symmetric stretching modes and the CCH ν(7)(+)(b(1)) out-of-plane bending mode of C(3)H(3)(+)(X(1)A(1)). The ν(5)(+)(a(1)) vibrational frequency of 1120 cm(-1) determined in the present study is lower than the value deduced from the recent Ar-tagged infrared photodissociation study by 102 cm(-1), confirming the highly accurate vibrational frequency predictions obtained by the most recent state-of-the-art ab initio quantum calculations. The observation of the FCF disallowed ν(7)(+)(b(1)) mode is indicative of vibronic interactions. The discrepancy observed between the FCF pattern determined in the present study and that predicted by a recent high-level quantum theoretical investigation can be taken as evidence that the potential energy surfaces used in the latter theoretical study are in need of improvement in order to provide a reliable FCF prediction for the C(3)H(3)/C(3)H(3)(+) photoionization system.