The propensity rules re-examined: Evidence for a long-lived complex in alkali diatomic-rare-gas collisions

When ΔJ =±1 collision-induced transitions in Π states of excited alkali diatomics are examined over a wide range of pressures several curious phenomena are observed. With the heavier rare gases we find that the ± propensities reverse as pressure increases, and the circular polarisation of the parent line first decreases, with increasing pressure and then begins to rise, the change-over occurring at roughly the same pressure as the reversal ΔJ =±1 collision propensities. A recently proposed theoretical model involving the formation of a long-lived atom—diatomic collision complex or Feschbach resonance is invoked to explain these unusual experimental results.     

The role of angular momentum in collision-induced vibration-rotation relaxation in polyatomics

Vibrational relaxation of the 6(1) level of S(1)((1)B(2u)) benzene is analyzed using the angular momentum model of inelastic processes. Momentum-(rotational) angular momentum diagrams illustrate energetic and angular momentum constraints on the disposal of released energy and the effect of collision partner on resultant benzene rotational excitation. A kinematic "equivalent rotor" model is introduced that allows quantitative prediction of rotational distributions from inelastic collisions in polyatomic molecules. The method was tested by predicting K-state distributions in glyoxal-Ne as well as J-state distributions in rotationally inelastic acetylene-He collisions before being used to predict J and K distributions from vibrational relaxation of 6(1) benzene by H(2), D(2), and CH(4). Diagrammatic methods and calculations illustrate changes resulting from simultaneous collision partner excitation, a particularly effective mechanism in p-H(2) where some 70% of the available 6(1)-->0(0) energy may be disposed into 0-->2 rotation. These results support the explanation for branching ratios in 6(1)-->0(0) relaxation given by Waclawik and Lawrance and the absence of this pathway for monatomic partners. Collision-induced vibrational relaxation in molecules represents competition between the magnitude of the energy gap of a potential transition and the ability of the colliding species to generate the angular momentum (rotational and orbital) needed for the transition to proceed. Transition probability falls rapidly as DeltaJ increases and for a given molecule-collision partner pair will provide a limit to the gap that may be bridged. Energy constraints increase as collision partner mass increases, an effect that is amplified when J(i)>0. Large energy gaps are most effectively bridged using light collision partners. For efficient vibrational relaxation in polyatomics an additional requirement is that the molecular motion of the mode must be capable of generating molecular rotation on contact with the collision partner in order to meet the angular momentum requirements. We postulate that this may account for some of the striking propensities that characterize polyatomic energy transfer.     

Collision dynamics of excited NaK. I. Reactive KNaK and elastic HeNaK collisions

The collision dynamics of excited NaK have been studied using the technique of circularly polarised laser fluorescence. A very unusual m-dependent rate is observed for KNaK* reactive or quenching collisions which is different depending on whether the initial excitation is via Q or P, R transitions. A model is presented attributing this to the spatial distribution of the ¹Π Λ-doublet components and the influence of the nuclear function. Elastic HeNaK collisions are observed and a reorientation cross section for f = 30 was evaluated. This was found to have an upper limit of 0.3 Ų. Comparison of this with HeLi₂ reorientation cross sections indicate that the presence of a permanent dipole moment has little effect on the reorientation rate in rare gas-alkali dimer collisions.     

Time-harmonic torsional waves in a composite cylinder with an imperfect interface

In this paper, the propagation of time-harmonic torsional waves in composite elastic cylinders is investigated. An imperfect interface is considered where tractions are continuous across the interface and the displacement jump is proportional to the stress acting on the interface. A frequency equation is derived for the rod and dispersion curves of normalized frequency as a function of normalized wave number for elastic bimaterials with varying values for the interface constant F are presented. The analysis is shown to recover the dispersion curves for a bimaterial rod with a perfect (welded) interface (F = 0), and has the correct limiting behavior for large F. It is shown that the modes, at any given frequency, are orthogonal, and it is outlined how the problem of reflection of a torsional mode by a planar defect (such as a circumferential crack) can be treated.     

Laser-interrogated dichroic spectroscopy: A sensitive probe of molecular anisotropies

A technique for measuring the parameters which characterise the anisotropic spatial distributions of angular momentum vectors of molecules in dilute ga     

Alignment of diatomic molecules by gaseous transport

Iodine molecules in a flow cell containing helium as a carrier gas appear to be partially aligned. This has been determined by comparison of circular polarisation ratios of rotationally resolved emission lines in the flow cell with those obtained from a similar cell containing 1₂ in an isotropic environment. After all other possibilities have been eliminated, two experimental indicators of alignment remain. One is the reduction of the absolute value of the circular polarisation ratio and the other is the differential reduction of one of the P,R-doublet emission lines.