Rotational relaxation studies in CO2 molecules by means of a multiline tea CO2 laser system

If a CO₂ laser amplifier is injected by a single-frequency oscillator, the efficiency is limited. A multiline pulsed oscillator has been developed to overcome this limitation.     

Electron scattering by atoms and molecules

Recent advances in the scattering of electrons by free atoms and molecules are considered with an emphasis on the interface between experiment and theory. A survey is made of the theory and methods of measurement and their trend towards the perfect scattering experiment. For atomic targets a detailed coverage is given of the various theoretical models and the results compared with experimental data. For elastic and excitation collisions, the low and high energy regions are reasonably well understood. In the medium energy region, extending from a few times the ionization threshold down to about the ionization threshold there are still difficulties arising from the infinite number of open channels. For ionizing collisions, the three body Coulomb interaction still presents unanswered theoretical problems but has inspired some elegant experimental studies. For molecular targets the additional complexities arising from the nuclear motion, the lack of a centre of symmetry and the evaluation of multicentre integrals are considered. A brief discussion of some current problems and possible future developments is given.     

Rotational diffusion and orientation relaxation of rodlike molecules in a biaxial liquid crystal phase

The longitudinal relaxation time and the complex dielectric polarizability of rod-like molecules with dipole moment parallel to the long axis in a biaxial nematic liquid crystal are calculated using as model the rotational Brownian motion in a mean field potential so reducing the problem to a solution of a set of linear differential-recurrence relations for statistical moments (the appropriate equilibrium orientational correlation functions). The solution of this set is obtained by matrix continued fractions. Moreover, simple analytic equations (based on the exponential separation of the time scales of the intrawell and overbarrier (interwell) relaxation processes), allowing one to understand the qualitative behavior of the system and accurately predicting the longitudinal complex polarizability for wide range of the barrier height and anisotropy parameters, are proposed.     

Reactions of excited atoms and molecules with atoms and molecules

Penning electron distributions arising from the ionization of Na and K by He (1s 2s ^1,3 S)-metastables in thermal collisions, as well as the absolute cross section for Penning ionization of Na by He (2³ S) and relative cross sections for ionization of Na and K by He(2¹ S) and He(2³ S) are measured. It is shown that under fairly general conditions the well depth ε* of the interaction potential between the metastable and the target particle can be obtained directly from the measured electron distributions. ε*-values are reported for the moleules He(1s 2s ^1,3 S)-Na(² S), K(² S) (^2,2Ω), and for He(1s 2s ^1,3 S)-Hg(¹ S)(^1,3Ω). These latter values are obtained from previously published measurements and are to be considered preliminary. Further, additional evidence is given, that Penning ionization with metastables is an electron exchange process.     

Reactions of excited atoms and molecules with atoms and molecules

From a He-beam excited by electron impact we eliminated the He(2¹ S) component to better than 0.5% by irradiating light from a He discharge. The quenching process ishv(2¹ P→2¹ S)+He(2¹ S)→He(2¹ P)→He(1¹ S +hv) (2¹ P 1)¹ S. By measuring the ions produced in collisions of the He-metastables with various target gases in a mass spectrometer, singlet to triplet Penning-cross section ratios were obtained. These ratios are without exception close to one, which is taken as evidence for the previously proposed electron exchange mechanism of the Penning ionization. In the case that more ions are produced in the collision of He (2¹ S) and He(2³ S) with a target gas, separate relative production cross sections are obtained for the two metastables. For the rare gases the measurements are performed at two temperatures of the He-beam, 320 and 90 °K. It is found that the cross section ratio of associative — to Penning ionization increases considerably as the temperature is decreased for both, He(2¹ S) and He(2³ S), the effect being much more pronounced for He(2¹ S). The results of this work are found to confirm conclusions drawn from measured energy distributions of the electrons ejected in the Penning process.     

Reactions of excited atoms and molecules with atoms and molecules

Ionizing collisions of long lived excited particles with atoms and molecules are studied by a cross beam technique. For the first time reactions of atoms in high Rydberg states are included in the investigation. In this paper we report relative cross sections for the production of the ions RH⁺, RH ₂ ⁺ , and H ₂ ⁺ by collisions of excited rare gas atoms R^* with H₂. With HD as the target molecule the isotope effect for the production of RD⁺ and RH⁺ has been determined. In the case of argon and krypton, ions are produced only by the high Rydberg states, whereas in the case of helium and neon only the metastable states contribute to a measurable extent. The data indicate, that the reaction mechanism is different in principle for metastable and highly excited atoms. Simple models are proposed to explain the experimental results.     

Rotational viscosity of uniaxial molecules

Non-equilibrium molecular dynamics (NEMD) are used to calculate the vortex or rotational viscosity of fluids composed of uniaxial molecules. It is shown that the NEMD homogeneous spin flow algorithm proposed by Edberg, R., Evans, D. J., and Moriss, G. P., 1987, Molec. Phys., 62, 1357 considerably underestimates the vortex viscosity. A modified version of this algorithm is proposed and applied to liquid chlorine and nitrogen. The results are in good agreement with previous work using equilibrium or other NEMD methods, and also show that at high spin rates the vortex viscosity decreases with increase in magnitude of the external torque used to drive the spin flow.     

Ionization of atoms and molecules by antiproton impact

During the decade that the LEAR accelerator at CERN has existed, the PS194 collaboration has obtained a substantial amount of experimental data for the ionization of atoms and molecules by antiproton impact. Here, we present a few of the most important and recent results, compare them to newly developed theory, and point out the progress that has been achieved for our understanding of ionization in few-body systems because of this information, as well as some remaining problems. PS194 collaboration at CERN This revised version was published online in August 2006 with corrections to the Cover Date.     

Rotational structures of long-range diatomic molecules

We present a systematic understanding of the rotational structure of a long-range (vibrationally highly-excited) diatomic molecule. For example, we show that depending on a quantum defect, the least-bound vibrational state of a diatomic molecule with -C _n /r ⁿ (n > 2) asymptotic interaction can have only 1, 2, and up to a maximum of n-2 rotational levels. A classification scheme of diatomic molecules is proposed, in which each class has a distinctive rotational structure and corresponds to different atom-atom scattering properties above the dissociation limit.Received: 15 June 2004, Published online: 28 September 2004PACS: 33.15.Mt Rotation, vibration, and vibration-rotation constants - 34.10. + x General theories and models of atomic and molecular collisions and interactions (including statistical theories, transition state, stochastic and trajectory models, etc.) - 03.75.Nt Other Bose-Einstein condensation phenomena - 03.75.Ss Degenerate Fermi gases     

Rotational relaxation rates in CO-He mixtures

The rotational level populations of CO molecules were measured in CO(<10%) + He free jets by electron beam fluorescence (in a stationary jet) and resonantly enhanced multiphoton ionization (in a pulsed jet). The measured evolution of the non-equilibrium rotational energy was used to derive the rotational relaxation cross-sections in the temperature range from 6 K to 140 K. To compare and analyse on a common basis all available experimental data (ours and others) on rotational relaxation of CO in He, the infinite order sudden approximation was explored. The following quantities were investigated: integral rotationally inelastic cross-sections, state-to-state rate coefficients, rotational relaxation times, line broadening coefficients, and non-equilibrium rotational energy distributions in a free jet.     

Rotational correlation functions of single molecules

Single molecule rotational correlation functions are analyzed for several reorientation geometries. Even for the simplest model of isotropic rotational diffusion our findings predict nonexponential correlation functions to be observed by polarization sensitive single molecule fluorescence microscopy. This may have a deep impact on interpreting the results of molecular reorientation measurements in heterogeneous environments.     

Scattering of atoms and molecules by an electromagnetic field

The scattering of atoms and molecules by the force of stimulated light pressure appearing in a standing wave is considered. It is shown that short (10^-8s) light pulses of tunable lasers can deviate resonance atoms through an angle of about 5°. A high selectivity of scattering is retained in a standing wave even in conditions of great saturation. Therefore the considered effect can be used for the separation of isotopes.     

Longitudinal relaxation time of aligned atoms

A detailed analysis is given of the expressions for the longitudinal relaxation time of a system of optically aligned atoms in a cylindrical or spherical cell. It is shown that the results obtained from this analysis may be valuable not only for relaxation processes in the radio frequency range (Zeeman or hyperfine structure) but also in optical spectroscopy (pair of levels connected by a magnetic dipole transition).     

Electron excitation in atoms and molecules by neutron-nucleus scattering

The quantum theory of electron stimulated desorption developed in two preceding papers is presented in a WKB like form and is applied to the desorption of hydrogen and oxygen from tungsten. Retunnelling processes are taken into account and manifest themselves in an imaginary part in the potential of the desorbing particles. This imaginary part together with a non zero width of the wavepacket leads to quantum effects in the motion of the desorbing particles modifying the corresponding classical results of the reduction factor and of the energy conservation. The modifications turn out to be quite large for hydrogen as well as for oxygen increasing the reduction factor by several orders of magnitude. The isotope effect also is changed appreciable. The parameters of the model are determined from corresponding experimental data such as vibrational levels of the adsorbates, the energy distribution of the desorbing particles and the reduction factor.