Classical trajectory study of rotationally inelastic scattering of two HF molecules

Classical trajectory calculations of the partial opacities and integral cross sections for rotationally inelastic collisions of HF—HF were carried out for the j₁ = 0,j₂ = 0 → (11), (02), (22) transitions at initial relative translational energies of 500, 1000, and 8000 cm^?1 and for the (11) → (02) transition at 1000 cm^?1. Three different methods of relating the initial and final quantum rotational levels to classical distributions were used. The results were compared to the quantum calculations of DePristo and Alexander. It was found that the classical method using a random distribution of initial rotational energies was in poor agreement with the quantum results, while the other two methods which assigned definite classical energies to the quantum levels were in good agreement with the quantum results.     

Vibrationally selective radiative and non-radiative transitions in gaseous hydrogen molecules

An efficient vibrationally selective technique to build-up the v″=1 vibrational levels in gaseous hydrogen is demonstrated using stimulated Raman pumping (SRP). Both photo-acoustic Raman spectroscopy (PARS) and coherent anti-Stokes Raman spectroscopy (CARS) are used to study non-radiative and radiative (v″=0 and v″=1) transitions in gaseous H(2) molecules. The population fraction in the v″=1 vibrational level has been estimated using combined photo-acoustic and coherent anti-Stokes Raman spectroscopy with stimulated Raman pumping.     

Rotationally inelastic scattering from surfaces HF(g) + LiF(001)

Rotationally inelastic scattering has been measured for a supersonic beam of HF off a clean LiF(001) surface, as a function of surface temperature and incident and final scattering angles. Rotational accomodation was found to be incomplete. Angular distributions were broad (substantially broader than cos θ_f) and independent of the rotational inelasticity.     

Initial relaxation times in dynamic light scattering from once-broken rod molecules in solution

Initial relaxation times determined by the initial decay rate of the time correlation function of scattered light are calculated for the once-broken rod model (two rigid rods of equal length connected by a universal joint) following the Fujiwara–Saito theory. The coefficient C describing the initial angular dependence of the first cumulant of the correlation function is also calculated. The results are compared with Pecora's results based on the Yu–Stockmayer theory for this model; and it is shown that the Fujiwara–Saito theory gives reasonable results.     

Deep inelastic scattering: Status and future

Deep inelastic lepton–nucleon scattering (DIS) is briefly characterised in its historical role in establishing the standard model of the electroweak and strong interactions. Key results are presented which are being obtained with the world's highest energy DIS experiments performed at HERA. Prospects are discussed for the future of DIS and experimentation with electron–proton beams approaching the TeV scale of energy in the next decade(s).     

Vibrationally inelastic collisions in H+ +CO system: comparing quantum calculations with experiments

State-resolved cross beam experiments [H. Udseth et al., J. Chem. Phys. 60, 3051 (1974); J. Krutein and F. Linder, J. Chem. Phys. 71, 599 (1979); G. Niedner-Schatteburg and J. P. Toennies, Adv. Chem. Phys. LXXXII, 553 (1992)], coupled with proton energy loss spectroscopy for the inelastic scattering of H(+) from CO in the collision range of 10-30 eV show very low vibrational excitation of the target molecule. Stimulated by the experimentally observed low vibrational inelasticity in the system the ground and the first two low-lying excited electronic potential-energy surfaces have been computed using the ab initio multireference configuration interaction method. Quantum dynamics has been performed on the ground potential energy surface in the framework of vibrational close-coupling rotational infinite-order sudden approximation. The various computed dynamical attributes such as differential and integral cross sections, and average vibrational energy transfer are analyzed in detail, and compared successfully with the available experimental results.     

Exponential perturbation theories for inelastic scattering

An Exponential Perturbation Theory (EPT) is derived whereby one calculates a phase-shift matrix by an nth order perturbation theory and then exponentiates it to obtain the scattering matrix. The theory has been developed to include high-order terms, closed channels and resonances. The radial wavefunctions used are WKB solutions which are generalized to cases where there are multiple turning points. The orbital angular momentum may be treated exactly or in the classical or sudden limits. Calculations are done for the rotationally inelastic scattering in He + H₂, Ar + N₂ and Ar + HCl. The first two systems give fair to good agreement with accurate calculations; the last case gives poor agreement. The first-order EPT is very much better than the first-order distorted-wave approximation.     

The k-j-j' vector correlation in inelastic and reactive scattering

Quasi-classical trajectory (QCT) methods are presented which allow characterization of the angular momentum depolarization of the products of inelastic and reactive scattering. The particular emphasis of the theory is on three-vector correlations, and on the connection with the two-vector correlation between the initial and final angular momenta, j and j', which is amenable to experimental measurement. The formal classical theory is presented, and computational results for NO(A) + He are used to illustrate the type of mechanistic information provided by analysis of the two- and three-vector correlations. The classical j-j' two-vector correlation results are compared with quantum mechanical calculations, and are shown to be in good agreement. The data for NO(A) + He support previous conclusions [M. Brouard, H. Chadwick, Y.-P. Chang, R. Cireasa, C. J. Eyles, A. O. L. Via, N. Screen, F. J. Aoiz, and J. K?os, J. Chem. Phys. 131, 104307 (2009)] that this system is only weakly depolarizing. Furthermore, it is shown that the projection of j along the kinematic apse is nearly conserved for this system under thermal collision energy conditions.     

Beam action spectroscopy via inelastic scattering

In this article, a new technique we call Beam Action Spectroscopy via Inelastic Scattering (BASIS) is demonstrated. BASIS takes advantage of the sensitivity of rotational state distributions in a supersonic molecular beam to inelastic scattering within the beam. We exploit BASIS to achieve increased sensitivity in two very different types of experiments. In the first, the UV photodissociation spectrum of OClO is recovered by monitoring intensity changes in the pure rotational transition of a spectator molecule (OCS) downstream from the nozzle, revealing a new vibrational structure in the region between 30,000 and 36,000 cm(-1). In the second, the mid-IR vibrational spectrum of acetylene is recorded simply by monitoring a single pure rotational transition of OCS co-expanded with acetylene. The technique may prove particularly fruitful when an excitation process produces product dark states that are not easily probed by conventional spectroscopy.     

Laser fluorescence studies of HF rotational relaxation

Rotation relaxation of HF in HF-Ar mixtures was observed using a laser infrared fluorescence technique. A specific vibrational-rotational state of HF was excited, and the fluorescence from HF was monitored. Total rotational energy-transfer rates, and individual state-to-state transition probabilities were obtained for υ = 1, J = 3 (ΔJ = ± 1, ±2) and υ = 1, J = 5; (ΔJ= ±1, ?2, ?3). The transition probabilities decreased with increasing ΔE_J,J, the energy transferred from R → T (rotation to translation). The data were fitted to a simple exponential model k_JJ, α exp(-ClΔE_J,J'l). C was estimated to be 1.55 ± 0.25 kcal^?1 mole.     

Quasielastic light scattering as a method for determining the distribution of relaxation times in a polymer system

Amongst other techniques, dynamic light scattering may be used to obtain molar mass distributions. The first step in this process consists in the Laplace inversion of the time correlation function that was measured by dynamic light scattering. This inversion gives a distribution of diffusion coefficients. In order to convert this distribution into the corresponding molar mass distribution, a relationship between diffusion coefficient and molar mass of monodisperse fractions has to be known. Such a relationship can be derived for linear and star-branched macromolecules from measurements of polydisperse systems, since the polydispersity of the distributions does not change with the molar mass. The problem is more involved with randomly branched materials, since in these cases the polydispersity increases strongly as the point of gelation is approached. A procedure is suggested for deriving the diffusion-molar mass dependence of monodisperse samples from polydisperse systems. After an outline of this background the method is applied to the three selected systems (i) radically polymerized linear PMMA, (ii) a star-branched microgel where monodisperse arms are attached to a microgel center and (iii) a randomly branched poly(dicyanate) sample based on bisphenol A. The results are compared with the combined column chromatography SEC/LALLS/VISC. Good agreement was found up to molar masses of about 10 millions g/mol, but systematic deviations occured in the high molar mass region. These differences result from the limitations of size permeation chromatography. Finally it is shown that the size distribution can be determind by this method, even for associates.     

A phase-corrected coupled-states approximation for inelastic scattering

A simple phase correction is derived for the coupled-states (CS) approximation based on WKB phase shifts for the electric part of the potential. The resulting phase-corrected CS (PCCS) scattering matrix agrees well in both phase and magnitude with the exact one. The PCCS approximation should then give accurate m-state information for any quantization axis.     

Oscillating term of the inelastic scattering factor

Formulas have been derived to calculate the factor of inelastic scattering of fast electrons by a molecular gas S(s) with inclusion of the chemical binding effect. In contrast to the free atoms approximation, the function S(s) has an oscillating term.Institute of High Temperatures, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 3, pp. 36–40, May–June 1993Translated by L. Smolina     

Collisional relaxation times in a three-level maser

We derive the Bloch equations for a three-level system, introducing phenomenological relaxation rates. Microscopic expressions are developed for these rates in the case of a gas of molecular absorbes for which relaxation is due to collisions with other molecules. Assuming that the colliding species move on classical paths and interact through long-range dipole terms, we can derive simple formulae for all the rates. A notable prediction is that certain off-diagonal rates are non-zero, though smaller than the diagonal terms. The physical significance of the results is briefly discussed.     

The inelastic neutron scattering spectrum of chloroform in solution

The incoherent inelastic neutron scattering (INS) spectrum of CHCl₃ in liquid SO₂ (ambient temperature) in the region 0–3600 cm⁻¹ is presented. For the first time it has been demonstrated that good quality INS data on solutes can be obtained over this energy transfer range. A discussion of suitable solvents for further work is included.     

Proton magnetic relaxation times and molecular motions in polydimethylsiloxane

The NMR relaxation times T₁ and T₂ have been measured for fractionated samples of polydimethylsiloxane with different molecular weights in the amorphous state and in tetrachloroethylene solutions. The results are interpreted on the basis of the anisotropic reorientation model proposed by Woessner for small molecules. A correlation time characteristic of the diffusional rotation of chain segments is calculated and shown to be proportional to the square root of the bulk viscosity.     

Elastic modulus and relaxation times in telechelic associating polymers

Dynamic mechanical measurements have been performed on solutions of HEUR-associating polymers with different molar mass, end-cap length, and extent of modification. These systems appear as Maxwellian fluids although at high frequencies a short-time relaxation process is evidenced for the systems with a strong hydrophobicity. This relaxation process could be attributed to the Rouse dynamics of active links in the temporary network. The high-frequency elastic modulus G_X decreases with increasing temperature according to an Arrhenius law. The associated activation energy decreases with increasing concentration. This is interpreted in terms of two contributions to the elastic modulus (osmostic and entropic elasticity).