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Journal of Chemical Physics, Vol.107, No.13, 4771-4782, 1997
Optical-optical double-resonance spectroscopic study of four ion-pair states of CIF and identification of the CIF(A(3)Pi(1)) valence state
Four of the six ion-pair states of CIF that correlate to Cl+(P-3(J)) and F-(S-1(0)), the E(0(+), P-3(2)), f(0(+), P-3(0)), beta(1, P-3(2)), and G(1, P-3(1)) states, have been identified by sequential, two-photon excitation via the CIF(B (3) Pi(0+)) valence state. The Omega=1 states, beta and G, were studied by selection of rotational levels of the B (3) Pi(0+) state that are perturbed by CIF(A (3) Pi(1)). Spectroscopic data from laser excitation and fluorescence spectra permit the assignment of vibrational energies and rotational constants to 30 levels. These four ion-pair states exhibit extensive homogeneous and heterogeneous interactions, and neither the vibrational energy nor the rotational constants are regular with increasing vibrational quantum number. The vibrational and rotational constants of the A (3) Pi(1) state were identified from the low resolution CIF[beta(1) - A (3) Pi(1)] emission spectra, and the dissociation limits of the A (3) Pi(1) and B (3) Pi(0+) states are compared. The dissociation energy of CIF(X) is confirmed to be 21110 cm(-1). Some qualitative information also was obtained about the D'(2, P-3(2)) and A' (3) Pi(2) states of CIF. (C) 1997 American Institute of Physics.