Journal of Chemical Physics, Vol.108, No.16, 6638-6651, 1998
The NO2 vibronic levels near the X(2)A(1)-A(2)B(2), conical intersection observed by laser induced dispersed fluorescence
Following our previous laser induced dispersed fluorescence (LIDFS) study on NO2 [J. Chem. Phys. 95, 5686 (1991)], we observed the vibronic levels up to 13900 cm(-1) by LIDFS. These observations allow one to characterize the effect of the conical intersection between the X (2)A(1) and A B-2(2) electronic potential energy surfaces (PESs). This effect has been investigated by ab initio methods in the same range by Leonardi et al. [J. Chem. Phys. 105, 9051 (1996)]. Globally we observed 420 vibronic levels of A(1) or B-2 symmetry up to 13900 cm(-1), while 259 were observed previously up to 12000 cm(-1). Most of these levels belong to the X (2)A(1) state and only 8 to the A B-2(2) state. Below 12000 cm(-1), most of the levels belonging to the X (2)A(1) state have been vibrationally assigned and only a few are significantly mixed with those of the A B-2(2) state. In contrast, each vibrational level of the A B-2(2) state is mixed with few nearby high vibrational levels of the X (2)A(1) state via vibronic interactions. The set of the X (2)A(1) vibrational levels is assigned and completed up to 11700 cm(-1) for the alpha(1) vibrational symmetry (171 levels) and up to 11000 cm(-1) for the b(2) symmetry (104 levels). Above these energies the X (2)A(1) - A B-2(2) vibronic interactions preclude secure vibrational assignment of most of the levels. The dominant electronic and vibrational characters have been used for the assignments of some levels. The set of zero order vibrational levels of the A B-2(2) State can be described by polyads because there is an approximate 2:1:2 ratio between the three vibrational frequencies. The four lowest polyads of B-2 vibronic symmetry are analyzed. In addition to the previously observed vibrationless level (0,0,0) of the A B-2(2) State (first polyad), the vibrational levels (0,1,0) (second polyad), (0,0,1) or (1,0,0), and (0,2,0) (third polyad) and (0,3,0) (belonging to the fourth polyad) have been observed. Numerous vibronic levels, previously observed by absorption (ICLAS) and/or by LIF, have also been observed by LIDFS. A semiquantitative analysis of these vibronic interactions is presented. The A and (B) over bar rotational constants of numerous vibrational levels have also been measured. Globally, these results allow a better understanding of the low energy range of X (2)A(1) - A B-2(2) vibronic interaction.
Keywords:POTENTIAL-ENERGY SURFACE;JET-COOLED NO2;VISIBLE EXCITATION SPECTRUM;THEORETICAL CHARACTERIZATION;AB-INITIO;ELECTRONIC-STRUCTURE;VIBRATIONAL LEVELS;NITROGEN-DIOXIDE;GROUND-STATE;HO2