Multiple-Photon Dynamics in Molecules: A New Approach to High Resolution Spectroscopy of Highly Excited Vibrational...

Multi-photon transitions with two simultaneously interacting IR laser fields lead to final excited states with frequencies nnu = n1nu1 + n2nu2, with n the total number of photons absorbed and (n, n1, n2) = (2, 1, 1), (3, 2, 1), (4, 1, 3), etc. The nature of the actual transition is determined by shift measurements, where the lasers are frequency-tuned by deltanui in opposite directions keeping the sum frequency, nnu, resonant with the molecular transition. This technique opens a new spectral range for multi-photon transitions and a unique identification of the observed features. For n1 and n2 both positive the excitation will lead to a "normal" up-up multi-photon transition. Many three- and four-photon transitions in the nu3 vibrational ladder of SF6 could be resolved with a resolution of 1 MHz, as well as four new two-photon transitions. As long as n1 + n2 >/= 0, one of the two ni may be negative resulting in an, e.g., up-down excitation pathway with its particular selection rules. The up-down excitations are demonstrated both for one- and two-photon transitions using the frequency shift technique. The different possible excitation schemes which meet the resonance condition for these transitions lead to interference effects and local couplings to highly excited states. Changes in resonance frequency for a one-photon transition (n = 1), due to these effects, are demonstrated. Evidently, the radiative coupling of participating levels to high-lying or quasi-continuum states may drastically change for different deltanui leading both to ac Stark shift and transition probability variations.