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Journal of Physics B Atomic Molecular and Optical Physics

Evidence for hybrid classical - quantal behaviour in state- and angle-resolved atom - diatom scattering

Anthony J. McCaffery, Ruth J. Wilson

Published Dec 28, 1997• 22 citations
Publisher

Abstract

We present measurements of the state-to-state differential scattering cross section (DCS) for X 16Cg Na2 with Xe using a new sub-Doppler spectroscopic method and compare results with those obtained using molecular beam techniques on the same system; the agreement is good. Criteria for comparison are based on the recent finding (McCaffery A J and Wilson R J 1996 Phys. Rev. Lett. 77 48) that simple quasiclassical vector relations determine the direction of the initial relative velocity vector and the scattering angle. The incident velocity direction is such that the perpendicular component just opens the inelastic channel and the parallel component is scattered. The relationship is Newtonian but is modified by the molecule’s characteristic quantum structure. Angular distributions from a range of experiments are found to obey the vector relation, suggesting that atom–molecule collisions are controlled by a quantum-modified Newtonian mechanics, the modification arising as a consequence of the internal energy level structure of the molecule. We introduce the term quantum-constrained kinematics to describe the hybrid mechanics and suggest that this may also influence other collisional events.

DOI
10.1088/0953-4075/30/24/015

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We present measurements of the state-to-state differential scattering cross section (DCS) for X 16Cg Na2 with Xe using a new sub-Doppler spectroscopic method and compare results with those obtained using molecular beam techniques on the same system; the agreement is good. Criteria for comparison are based on the recent finding (McCaffery A J and Wilson R J 1996 Phys. Rev. Lett. 77 48) that simple quasiclassical vector relations determine the direction of the initial relative velocity vector and the scattering angle. The incident velocity direction is such that the perpendicular component just opens the inelastic channel and the parallel component is scattered. The relationship is Newtonian but is modified by the molecule’s characteristic quantum structure. Angular distributions from a range of experiments are found to obey the vector relation, suggesting that atom–molecule collisions are controlled by a quantum-modified Newtonian mechanics, the modification arising as a consequence of the internal energy level structure of the molecule. We introduce the term quantum-constrained kinematics to describe the hybrid mechanics and suggest that this may also influence other collisional events.
[ACCESS RESTRICTED TO THE UNIVERSITY OF MISSOURI AT REQUEST OF AUTHOR.] This thesis presents the successful implementation of a slice velocity map imaging apparatus capable of performing molecular beam scattering experiments at collision energies from well above the room temperature to below 1 K. The novel techniques introduced here offers a platform to study collisions at a regime where the scattering is mainly governed by quantum mechanics. Experimental developments of low energy collisions will challenge the theoretical description of molecular interactions, and aid in validating the accuracy of the calculated potential energy surfaces. Scattering studies involving two different configurations of the apparatus, intrabeam and near-copropagating beam configurations are reported in this thesis. The intrabeam scattering approach exploits beam slippage, the velocity difference of different species in the same beam, to establish the relative velocity. The beam slippage in the current setup was created by a pulsed electric discharge which induced a velocity upchirp in the excited species. Implementing a unique dual-slit chopper that can separately fix the velocities of the excited and non-excited species at the interaction region, we achieve precise control over the relative velocity and narrow its spread. With this configuration l-changing collisions occurring between Xe Rydberg atoms and Xe ground state atoms at subKelvin temperatures have been observed. The near-copropagating beam apparatus coupled with the stimulated emission pumping method and sliced velocity map imaging detection enabled us to measure the state-to-state differential cross sections for inelastic collisions between vibrationally excited NO molecules and Ar at broadly tunable energies. Experimentally measured rotationally inelastic state-to-state differential cross sections have enjoyed excellent agreement with quantum scattering calculations performed on state-of-the-art coupled-cluster potential energy surfaces. In contrast, state-to-state differential cross sections obtained for collision-induced multiplet changing transitions at collision energies near 1 K have showed better agreement with quantum scattering calculations involving multireference potential energy surfaces compared to coupled-cluster surfaces. This study provided a platform to validate the accuracy of the potential energy surfaces for collisions which are mainly governed by the attractive part of the interaction potential.
As a further theoretical study of the collision-induced quantum interference on rotational energy transfer in an atom-diatom system, the differential interference angles for singlet-triplet mixed states of Na 2 system in collision with He were calculated based on the first-Born approximation of time-dependent perturbation theory, taking into account the anisotropic Lennard-Jones interaction potential and the long-range interaction potential.The relationships of differential interference angle versus impact parameter including collision parameter, velocity, are obtained.It is beneficial to reduce the loss in molecular cooling and trapping.
The amount of information that can be obtained from a scattering experiment depends upon the precision with which the quantum states are defined in the incoming channel. By precisely defining the incoming states and measuring the outgoing states in a scattering experiment, we set up the boundary condition for experimentally solving the Schrödinger equation. In this Perspective we discuss cold inelastic scattering experiments using the most theoretically tractable H 2 and its isotopologues as the target. We prepare the target in a precisely defined rovibrational ( v, j, m ) quantum state using a special coherent optical technique called the Stark-induced adiabatic Raman passage (SARP). v and j represent the quantum numbers of the vibrational and rotational energy levels, and m refers to the projection of the rotational angular momentum vector j on a suitable quantization axis in the laboratory frame. Selection of the m quantum numbers defines the alignment of the molecular frame, which is necessary to probe the anisotropic interactions. For us to achieve the collision temperature in the range of a few degrees Kelvin, we co-expand the colliding partners in a mixed supersonic beam that is collimated to define a direction for the collision velocity. When the bond axis is aligned with respect to a well-defined collision velocity, SARP achieves stereodynamic control at the quantum scale. Through various examples of rotationally inelastic cold scattering experiments, we show how SARP coherently controls the dynamics of anisotropic interactions by preparing quantum superpositions of the orientational m states within a single rovibrational ( v, j ) energy state. A partial wave analysis, which has been developed for the cold scattering experiments, shows dominance of a resonant orbital that leaves its mark in the scattering angular distribution. These highly controlled cold collision experiments at the single partial wave limit allow the most direct comparison with the results of theoretical computations, necessary for accurate modeling of the molecular interaction potential.
As a further theoretical study of the collision-induced quantum interference on rotational energy transfer in an atom-diatom system, the differential interference angles for singlet-triplet mixed states of Na 2 system in collision with He were calculated based on the first-Born approximation of time-dependent perturbation theory, taking into account the anisotropic Lennard-Jones interaction potential and the long-range interaction poten- tial. The relationships of differential interference angle versus impact parameter including collision parameter, velocity, are obtained. It is beneficial to reducing the loss in molecular cooling and trapping.
The close coupling calculation of rotationally inelastic collision of He with Na2 is first performed by employing a recently computed ab initio potential energy surface. The process of rovibrational energy excitation and relaxation of Na2 in collision with He has been studied in detail based on the single and double exitations coupled cluster with a noniterative perturbation treatment of triple excitations CCSD (T) potential energy surface. Our results are in good agreement with the experimental results. Our results show that: (1)The elastic cross section(Δj=0) is much larger than the inelastic cross section. (2)The largest amplitude occurs at small scattering angles. At low Δj transition, the He projectile is predominantly forward scattering. Backward scattering occurs as Δj increases. (3)For inelastic cross section, the most effective transition is that with Δj=2.(4)The fast narrow diffraction oscillations in the cross sections are the obvious characteristics for the low Δj inelastic transitions, which decreases with increasing j. (5)The elastic differential-cross-sections(DCS)provides a useful visualization of rotational rainbows at low translational energy. It is beneficial to reducing the loss in molecular cooling and trapping.