Diradicals, antiaromaticity, and the pseudo-Jahn-Teller effect: electronic and rovibronic structures of the...

The electronic and rovibronic structures of the cyclopentadienyl cation (C(5)H(5) (+)) and its fully deuterated isotopomer (C(5)D(5) (+)) have been investigated by pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectroscopy and ab initio calculations. The vibronic structure in the two lowest electronic states of the cation has been determined using single-photon ionization from the X (2)E(1) (") ground neutral state and 1+1(') resonant two-photon ionization via several vibrational levels of the A (2)A(2) (") excited state. The cyclopentadienyl cation possesses a triplet ground electronic state (X(+) (3)A(2) (')) of D(5h) equilibrium geometry and a first excited singlet state (a(+) (1)E(2) (')) distorted by a pseudo-Jahn-Teller effect. A complete analysis of the Emultiply sign in circlee Jahn-Teller effect and of the (A+E)multiply sign in circlee pseudo-Jahn-Teller effect in the a(+) (1)E(2) (') state has been performed. This state is subject to a very weak linear Jahn-Teller effect and to an unusually strong pseudo-Jahn-Teller effect. Vibronic calculations have enabled us to partially assign the vibronic structure and determine the adiabatic singlet-triplet interval (1534+/-6 cm(-1)). The experimental spectra, a group-theoretical analysis of the vibronic coupling mechanisms, and ab initio calculations were used to establish the topology of the singlet potential energy surfaces and to characterize the pseudorotational motion of the cation on the lowest singlet potential energy surface. The analysis of the rovibronic photoionization dynamics in rotationally resolved spectra and the study of the variation of the intensity distribution with the intermediate vibrational level show that a Herzberg-Teller mechanism is responsible for the observation of the forbidden a(+) (1)E(2) (')<--A (2)A(2) (") photoionizing transition.