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Journal of Chemical Physics, Vol.107, No.24, 10365-10372, 1997
Laser velocity modulation spectroscopy of TiCl+: Observation of the A (3)Delta(3d(2)) state and deperturbation of the X (3)Phi-A(3)Delta complex
A single mode cw dye laser along with velocity modulation was used to record weak bands of TiCl+ in the spectral region 17100-18600 cm(-1). The ions were produced in the positive column of an ac glow discharge with a gas mixture of He/TiCl4. These new bands have been identified as Linking the upper already known [17.8](3) Delta(3d4s) state to respectively the X-3 Phi(v = 1) state and to a newly observed A(3) Delta(v = 0) state located 350 cm(-1) above the X-3 Phi(v = 0) state. As suggested by Focsa ct al. (J. Chem. Phys. 106, 9044 (1997)) the A(3) Delta(3d(2)) State was found to be responsible for the perturbations observed in the X-3 Phi(3d(2)) state, The spin-orbit components of the A(3) Delta(v = 0) and the X-3 Phi(v = 1) states revealed interaction leading to homogeneous and heterogeneous perturbations, A set of deperturbed parameters has been determined with the help of a full matrix-based handling of the A(3) Delta(v = 0) and the X-3 Phi(v = 0,1) states. Study of the contributions of the basis functions to the eigenvectors of the diagonalized matrix displayed evidence of a reversal of the leading character of the Omega = 3 spin-orbit components of the A(3) Delta(v = 0) and the X-3 Phi(v = 1) states. A remarkable example of avoided crossing has been observed between the A(3) Delta(1)(v = 0)and the X-3 Phi(2)(v = 1) spin-orbit components. (C) 1997 American Institute of Physics.