Absorption cross sections and correlation functions of the NH2 A 2A1-X2B1 Renner-Teller system.
We present a quantum-mechanical study of absorption cross sections and correlation functions of the title system, using a spinless Hamiltonian that includes the nonadiabatic Renner-Teller (RT) coupling between the electronic states, and taking into account the nuclear-spin statistics. We consider also the stimulated emission, assuming a Boltzmann distribution of the molecular levels, and we express correlation functions in terms of wave-packet (WP) overlaps. Assuming that the body-fixed z component of the angular momentum is a constant of motion of isolated NH(2), we calculate X rotational and rovibrational, and X+A rovibronic cross sections and correlation functions at 4.2 and 300 K, up to 26 000 cm(-1) and 3000 fs. We also report the rotational spectrum at 3000 K. The number of absorbing states is large at high T, and the number of lines with appreciably intensity thus increases remarkably with T, from 67 at 4.2 K, to 847 at 300 K, and up to 10 609 at 3000 K. The cold spectrum consists only of Pi lines, due to ground-level absorption. At room and higher T, the hot spectrum presents long progressions of rovibronic lines. The strongest spectral intensities are X Pi and Phi rotational lines and A bending Sigma and Pi lines. We also find many Fermi resonances between A bending and combination states, and that approximately 50% of the lines belong to both electronic states. This latter result points out many RT couplings above 11 000 cm(-1). The theoretical intensities agree very well with the few available experimental data. The time evolution of the correlation functions reflects all internal motions, with periods ranging from approximately 750 to 2 fs, from slow rotational modes to ultrafast electronic dynamics. At low T, the correlation function is proportional to the survival probability of an initial WP, it has many recursions, and can be very regular, without decaying on the average. At high T, the correlation function is associated with the dynamics of many WPs, which present different dephasing times, and the dynamics thus becomes very irregular. The internal dynamics is nonadiabatic above 11 000 cm(-1), because the WPs move from the vertical to the linear region of the excited surface, and can jump to the ground surface owing to RT couplings.
Petrongolo
Carlo
C
Dipartimento di Chimica, Università di Siena, Via Aldo Moro 2, I-53100 Siena, Italy. petrongolo@unisi.it