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 a s Linking the upper already known [17.8](3) Delta(3d4s) state to respe ctively 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 sugge sted 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 observe d in the X-3 Phi(3d(2)) state, The spin-orbit components of the A(3) D elta(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 ha ndling 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 th e 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 cro ssing has been observed between the A(3) Delta(1)(v = 0)and the X-3 Ph i(2)(v = 1) spin-orbit components. (C) 1997 American Institute of Phys ics.