Collision energy dependence of state-to-state differential cross sections for rotationally inelastic scattering of H2O by He.

The inelastic scattering of H2O by He as a function of collision energy in the range 381 cm-1 to 763 cm-1 at an energy interval of approximately 100 cm-1 has been investigated in a crossed beam experiment using velocity map imaging. Change in collision energy was achieved by varying the collision angle between the H2O and He beam. We measured the state-to-state differential cross section (DCS) of scattered H2O products for the final rotational states JKaKc = 110, 111, 221 and 414. Rotational excitation of H2O is probed by (2 + 1) resonance enhanced multiphoton ionization (REMPI) spectroscopy. DCS measurements over a wide range of collision energies allowed us to probe the H2O-He potential energy surface (PES) with greater detail than in previous work. We found that a classical approximation of rotational rainbows can predict the collision energy dependence of the DCS. Close-coupling quantum mechanical calculations were used to produce DCS and partial cross sections. The forward-backward ratio (FBR), is introduced here to compare the experimental and theoretical DCS. Both theory and experiments suggest that an increase in the collision energy is accompanied with more forward scattering.

The Jahn-Teller effect in the presence of partial isotopic substitution: the B̃(1)E'' state of NH2D and NHD2.

Rotationally resolved resonance enhanced multiphoton ionisation spectra of the B̃(1)E'' state of NH2D are presented and analysed. The analysis indicates a small (34.9 cm(-1)) lifting of the vibronic degeneracy of the zero point level, approximately equal in sign but opposite in magnitude to the splitting observed in NHD2 in previous work. This observation is consistent with previous measurements on systems with partial isotopic substitution subject to a mild Jahn-Teller effect. A model is developed to calculate the splitting induced by asymmetric isotopic substitution of a degenerate electronic state, based on a harmonic force field with linear and quadratic Jahn-Teller terms added. The force field is developed in internal co-ordinates to allow the same parameters to be used to calculate the pattern of vibronic levels for all four isotopologues. The lifting of the degeneracy of the zero point level on asymmetric substitution comes from the quadratic Jahn-Teller effect; the linear term does not lift the degeneracy.

Differential and integral cross sections in OH(X) + Xe collisions.

Differential cross sections (DCSs) for inelastic collisions of OH(X) with Xe have been measured at a collision energy of 483 cm(-1). The hydroxyl (OH) radicals were initially prepared in the X(2)Π3/2 (v = 0, j = 1.5, f) level using the hexapole electric field selection method. Products were detected state-selectively by [2 + 1] resonance-enhanced multiphoton ionization of OH, combined with velocity-map imaging. Integral cross sections in OH(X) + Xe at a collision energy of 490 cm(-1) were also measured by laser-induced fluorescence. The results are compared with exact close-coupling quantum mechanical scattering calculations on the only available ab initio potential energy surface (PES). The agreement between experimental and theoretical results is generally very satisfactory. This highlights the ability of such measurements to test the available PES for such a benchmark open-shell system. The agreement between experiment and theory for DCSs is less satisfactory at low scattering angles, and possible reasons for this disagreement are discussed. Finally, theoretical calculations of OH(X) + He DCSs have been obtained at various collision energies and are compared with those of OH(X) + Xe. The role of the reduced mass in the DCSs and partial cross sections is also examined.

State-to-state resolved differential cross sections for rotationally inelastic scattering of ND3 with He.

State-to-state differential cross sections are reported for rotationally inelastic scattering of fully state-selected ND3 (j(k)(±) = 1(1)(-)) with He. Experimental measurements are compared with full close-coupling quantum-mechanical scattering calculations that used an ab initio potential energy surface. Results are presented for final states up to j'(k')(±) = 7(7)(-) at a mean collision energy of 430 cm(-1). For selected final quantum states, the effect of collision energy on the differential cross sections is also explored in the range 230-720 cm(-1). For the experimental studies, a hexapole electrostatic lens was used for the j(k)(±) state-selection of ND3 molecules in their electronic and vibrational ground states in a molecular beam. This state-selected molecular beam was then crossed with a beam of He atoms. The velocities of inelastically scattered ND3 molecules in single j'(k')(±) states were obtained by velocity map imaging, and converted to differential cross sections in the centre-of-mass frame by density-to-flux transformation. The close-coupling calculations reproduce well the measured angular distributions. For small changes in the rotational angular momentum quantum number (j), the ND3 is predominantly forward scattered, but the scattering shifts to the sideways and backward directions as Δj increases. For scattering into a given j'(k')(±) state, cross-sections for collisions that conserve the ± symmetry associated with the ND3 inversion vibration are larger and generally more forward scattered than the corresponding symmetry-changing processes.

Resonance enhanced multiphoton ionization spectroscopy of NHD2 via the B1E''-state.

Rotational analysis of the (2 + 1) resonance enhanced multiphoton ionization (REMPI) spectrum of the B[combining tilde](1)E'' Rydberg state of the ammonia isotopologue NHD2 is reported. While the electronic degeneracy is lifted in NHD2 the splitting is small enough that interactions between the two states must be considered, particularly to model the intensity of the transitions. A simple model is developed to account for these interactions, relating them to terms present in the symmetric isotopologues. Spectroscopic parameters for the zero point and (ν2' = 1-6) vibrational levels of the B (1)E'' state have been derived using this model and the spectra are accurately simulated for the first time using the pgopher program. The current work provides the basis for on-going velocity map imaging studies of rotational energy transfer in the mixed isotopologues of ammonia.

Rotational excitation of HDO and D2O by H2: experimental and theoretical differential cross-sections.

We present state-to-state differential cross sections (DCSs) for rotationally inelastic scattering of HDO by normal- and para-H(2) at collision energies of 580 cm(-1) and 440 cm(-1). (2+1) resonance enhanced multiphoton ionization is used to detect rotationally cold HDO molecules before collision and as scattering products, which occupy higher rotational states due to collision with H(2). Relative integral cross sections of HDO are obtained by integrating its DCSs measured at the same experimental conditions. Experimental and theoretical DCSs of HDO scattered by normal- and para-H(2) are in good agreement in 30°-180° range of scattering angles. This partial agreement shows the accuracy of the recently tested potential of H(2)O-H(2), but now by using a completely different set of rotational transitions that are (unlike in H(2)O), not forbidden by nuclear spin restrictions. Similar results are presented for D(2)O scattered by normal-H(2) at collision energy of 584 cm(-1). The agreement between experiment and theory is, however, less good for forward scattering of HDO/D(2)O. A critical analysis of this discrepancy is presented.