Photodissociation of [Ar-N] induced by near-IR femtosecond laser fields by ion-trap time-of-flight mass spectrometry.

Photodissociation of [Ar-N] induced by a near-IR (800 nm) femtosecond laser pulse is investigated using ion-trap time-of-flight mass spectrometry. The intra-complex charge transfer proceeding in the course of the decomposition of the electronically excited Ar(P)⋯N(XΣ ), prepared by the photoexcitation of the electronic ground Ar(S)⋯N (XΣ ), is probed by the ion yields of Ar and N . The yield ratio γ of N with respect to the sum of the yields of Ar and N is determined to be γ = 0.62, which is much larger than γ ∼ 0.2 determined before when the photodissociation is induced by a nano-second laser pulse in the shorter wavelength region between 270 and 650 nm. This enhancement of γ at 800 nm and the dependence of γ on the excitation wavelength are interpreted by numerical simulations, in which the adiabatic population transfer from Ar(P)⋯N(XΣ ) to Ar(S)⋯N (XΣ ) at the avoided crossings is accompanied by the vibrational excitation in the N (XΣ ) moiety followed by the intra-complex vibrational energy transfer from the N (XΣ ) moiety to the intra-complex vibrational mode leading to the dissociation.