Long time scale dynamics of vibrationally excited (HBr)n clusters.

We investigated the photodissociation dynamics of vibrationally excited HBr molecules and clusters. The species were generated in a molecular beam and excited with an IR laser to a v = 1 vibrational state. A subsequent ultraviolet (UV)-pulse with 243 nm radiation photolysed the molecules to yield H-fragments, which were resonantly ionized by the same UV-pulse (2 + 1 REMPI) and detected in a velocity map imaging (VMI) experiment. We performed action spectroscopy to distinguish between two expansion regimes: (i) expansion leading to isolated HBr molecules and (ii) generation of large (HBr)n clusters. Photodissociation of isolated HBr ( v = 1) molecules in particular J ro-vibrational states yielded faster H-fragments (by approximately 0.3 eV) with respect to the photodissociation of the ground state HBr ( v = 0). On the contrary, the IR excitation of molecules in (HBr) n clusters enhanced the yield of the H-fragments UV-photodissociated from the ground-state HBr ( v = 0) molecules. Our findings show that these molecules are photodissociated within clusters, and they are not free molecules evaporated from clusters after the IR excitation. Nanosecond IR-UV pump-probe experiments show that the IR-excitation enhances the H-fragment UV-photodissociation yield up to ∼100 ns after the IR excitation. After these long IR-UV delays, excitation of HBr molecules in clusters does not originate from the IR-excitation but from the UV-photodissociation and subsequent caging of HBr molecules in v > 0 states. We show that even after ∼100 ns the IR-excited larger (HBr) n clusters do not decay to individual molecules, and the excitation is still present in some form within these clusters enhancing their UV-photodissociation.

Imaging of rotational wave-function in photodissociation of rovibrationally excited HCl molecules.

We demonstrate a visualization of quantum mechanical phenomena with the velocity map imaging (VMI) technique, combining vibrationally mediated photodissociation (VMP) of a simple diatomic HCl with the VMI of its H-photofragments. Free HCl molecules were excited by a pump infrared (IR) laser pulse to particular rotational J levels of the v = 2 vibrational state, and subsequently a probe ultraviolet laser photodissociated the molecule at a fixed wavelength of 243.07 nm where also the H-fragments were ionized. The molecule was aligned by the IR excitation with respect to the IR laser polarization, and this alignment was reflected in the angular distribution of the H-photofragments. In particular, the highest degree of molecular alignment was achieved for the J=1←0 transition, which exclusively led to the population of a single rotational state with M = 0. The obtained images were analyzed for further details of the VMP dynamics, and different J states were studied as well. Additionally, we investigated the dynamic evolution of the excited states by changing the pump-probe laser pulse delay; the corresponding images reflected dephasing due to a coupling between the molecular angular momentum and nuclear spin. Our measurements confirmed previous observation using the time-of-flight technique by Sofikitis et al. [J. Chem. Phys. 127, 144307 (2007)]. We observed a partial recovery of the originally excited state after 60 ns in agreement with the previous observation.