Master equations for photochemistry with intense infrared light (III) the influence of molecular parameters in URIMIR

Abstract

The influence of molecular parameters on the rate of unimolecular reactions induced by monochromatic infrared radiation (URIMIR) is considered in the range of validity of a Pauli master equation. Solutions of the master equation are obtained for a model series of bond fission reactions. A two parameter activation equation for the time dependent rate coefficient is established. The dependence of the steady state rate coefficient, the activation time, and further relevant rate parameters upon the threshold energy for reaction, the excitation quantum, the number of vibrational modes, and the integrated oscillator strength of the fundamental transition is established and summarized in three simple rules. Quantitative calculations for the case B intensity fall‐off are presented. The possibility of an absolute estimate of the rate parameters is discussed with the example of the URIMIR of CF3I.

Stereomutation dynamics in hydrogen peroxide

“…Particularly after the discovery [7][8][9] and theoretical description [10][11][12][13] of isotope selective coherent infrared multiphoton excitation and laser chemistry of polyatomic molecules and subsequently also the advent of ''Femtosecond Chemistry'' [14,15] there has been much interest in what has been called in a variety of contexts either ''mode selective chemistry'' [16,17] or reaction control [18][19][20][21] including chiral molecules [22,23]. This question has been addressed from a variety of points of view, and Jö rn Manz and his group have been early players in the field, including both bimolecular and unimolecular reactions [24][25][26].…”