Collisional and Radiative Effects in Transient sub-Doppler Hole Burning: Double Resonance Measurements in CN

We report transient hole-burning and saturation recovery measurements in the CN radical with MHz frequency resolution and 20 ns time resolution. Narrow velocity groups of individual hyperfine levels of selected rotational states in CN (X{sup 2} {Sigma}{sup +}) are depleted and excited (A{sup 2}{pi}{sub i}) with a saturation laser and probed by a counterpropagating, frequency modulated probe beam. Recent work in our lab has used this method to measure and characterize the hyperfine splittings for a set of rotational, fine structure, and parity components of CN (A{sup 2}{pi}{sub i}, v=1). Extending this work, we report time and frequency dependence of the saturation signals following abrupt switching of the CW saturation beam on and off with an electro-optic amplitude modulator. Recovery of the unsaturated absorption following the turnoff of the saturation beam follows pressure-dependent kinetics, driven by collisions with the undissociated NCCN precursor with a rate coefficient of 2 x 10{sup -9} cm{sup 3} s{sup -1} molec{sup -1}. Similar recovery kinetics are observed for two-level saturation resonances, where the signal observed is a combination of X- and A-state kinetics, as well as for three-level crossover resonances, which can be chosen to probe selectively the holefilling in the X state or the decay of velocity-selected A state radicals. The observed recovery rates are 8-10 times faster than the estimated rotationally inelastic contribution. The observed recovery rates are likely dominated by velocity-changing collisions in both X and A states, occurring with similar rates, despite the large difference in the properties of these electronic states. Transient signal risetimes following the turning on of the saturation pulse are consistent with the expected Rabi frequency. At lower pressures ({approx}50 mTorr) and higher beam power ({approx}200 mW), we can observe multiple Rabi cycles before collisions disrupt the coherent excitation and the transient signal reaches a steady state

Neutron scattering and molecular correlations in a supercooled liquid

We show that the intermediate scattering function $S_n(q,t)$ for neutron scattering (ns) can be expanded naturely with respect to a set of molecular correlation functions that give a complete description of the translational and orientational two-point correlations in the liquid. The general properties of this expansion are discussed with special focus on the $q$-dependence and hints for a (partial) determination of the molecular correlation functions from neutron scattering results are given. The resulting representation of the static structure factor $S_n(q)$ is studied in detail for a model system using data from a molecular dynamics simulation of a supercooled liquid of rigid diatomic molecules. The comparison between the exact result for $S_n(q)$ and different approximations that result from a truncation of the series representation demonstrates its good convergence for the given model system. On the other hand it shows explicitly that the coupling between translational (TDOF) and orientational degrees of freedom (ODOF) of each molecule and rotational motion of different molecules can not be neglected in the supercooled regime.Further we report the existence of a prepeak in the ns-static structure factor of the examined fragile glassformer, demonstrating that prepeaks can occur even in the most simple molecular liquids. Besides examining the dependence of the prepeak on the scattering length and the temperature we use the expansion of $S_n(q)$ into molecular correlation functions to point out intermediate range orientational order as its principle origin.Comment: 13 pages, 7 figure

Gas-Phase Molecular Dynamics: High Resolution Spectroscopy and Collision Dynamics of Transient Species

This research is carried out as part of the Gas-Phase Molecular Dynamics program in the Chemistry Department at Brookhaven National Laboratory. High-resolution spectroscopy, augmented by theoretical and computational methods, is used to investigate the structure and collision dynamics of chemical intermediates in the elementary gas-phase reactions involved in combustion chemistry. Applications and methods development are equally important experimental components of this work