Journal of Chemical Physics, Vol.120, No.14, 6439-6448, 2004
Sub-Doppler rotationally resolved spectroscopy of lower vibronic bands of benzene with Zeeman effects
Sub-Doppler high-resolution excitation spectra and the Zeeman effects of the 6(0)(1), 1(0)(1)6(0)(1), and 1(0)(2)6(0)(1) bands of the S-1 B-1(2u)<--S-0 (1)A(1g) transition of benzene were measured by crossing laser beam perpendicular to a collimated molecular beam. 1593 rotational lines of the 1(0)(1)6(0)(1) band and 928 lines of the 1(0)(2)6(0)(1) band were assigned, and the molecular constants of the excited states were determined. Energy shifts were observed for the S-1 B-1(2u)(v(1)=1,v(6)=1,J,Kl=-11) levels, and those were identified as originating from a perpendicular Coriolis interaction. Many energy shifts were observed for the S-1 B-1(2u)(v(1)=2,v(6)=1,J,Kl) levels. The Zeeman splitting of a given J level was observed to increase with K and reach the maximum at K=J, which demonstrates that the magnetic moment lies perpendicular to the molecular plane. The Zeeman splittings of the K=J levels were observed to increase linearly with J. From the analysis, the magnetic moment is shown to be originating mostly from mixing of the S-1 B-1(2u) and S-2 B-1(1u) states by the J-L coupling (electronic Coriolis interaction). The number of perturbations was observed to increase as the excess energy increases, and all the perturbing levels were found to be a singlet state from the Zeeman spectra. (C) 2004 American Institute of Physics.