Resonant charge exchange in slow collisions involving halogens and oxygen

The coupling of electron momenta is considered for the resonant charge exchange process in slow collisions. Because the electron transfer in this process occurs at large distances between the colliding atomic particles, where ion-atom interactions are relatively weak, we can separate different types of interaction and find the character of coupling of the electron momenta in the quasi-molecule, consisting of the colliding ion and its atom, for real collision pairs. Since the real number of interaction types for colliding particles exceeds that used in the classical Hund coupling scheme, there are intermediate cases of momentum coupling outside the standard Hund scheme. This occurs for the resonant charge exchange involving halogens and oxygen where the quantum numbers of the quasi-molecule in the course of the electron transfer are the total momenta J and j of the colliding ion and atom and the projection M or M_J of the atom orbital or total momentum on the quasi-molecule axis. The ion-atom exchange interaction potential is independent of the ion fine state, and under these conditions, the resonant charge exchange process is not entangled with the rotation of electron momenta, as in case “a” of the Hund coupling. The partial cross section of the resonant charge exchange process depends on quantum numbers of the colliding particles. The average cross sections depend weakly on the coupling scheme.     

Temperature Dependence of the Vibrational Relaxation Rate Constants of CO2 (0001) in Binary Mixtures

The rate constants of intramolecular intermode relaxation of the CO₂ molecule (00⁰1) in pure CO₂ and in binary mixtures with He, Ar, H₂, O₂, N₂, CO, NO, N₂O, and H₂O were measured in the temperature range 300–1000 K by means of a laser-induced luminescence method. It is shown that these relaxation rate constants K for all the gas mixtures investigated increase with increase in the gas temperature in this range; the most efficient in deactivation of the 00⁰1 level are the collisions of CO₂ molecules with H₂O molecules; the mechanisms of relaxation of the 00⁰1 level of CO₂ and their channels depend not only on the temperature but also on the parameters of colliding particles; for each of the colliding partners of the CO₂ molecules there is a certain temperature T _c above which the temperature dependence of K is coordinated with the Landau–Teller dependence, and, moreover, the simpler the structure of the colliding partner of the CO₂ molecule, the higher the temperature T _c. Deviations from these dependences at temperatures T < T _c are attributed to the influence of intermolecular forces of attraction, change of relaxation channels, and formation of molecular clusters. For all the colliding partners of the CO₂ molecules, the interaction radii are determined from the intermolecular potentials of interaction used in the theoretical model.     

Born-Oppenheimer breakdown effects and hyperfine structure in the rotational spectra of SbF and SbCl

Pure rotational spectra have been measured for the ground electronic states of SbF and SbCl. The molecules were prepared by laser ablation of Sb metal in the presence of SF₆ or Cl₂, respectively. Their spectra were measured with a cavity pulsed jet Fourier transform microwave spectrometer. Although both molecules have two unpaired electrons, they are subject to Hund’s coupling case (c), and have X₁0⁺ ground states. The spectra have been interpreted with the formalism of ¹Σ⁺ molecules. For both molecules spectra of several isotopomers have been measured in the ground and first excited vibrational states. Large hyperfine splittings attributable to both nuclear quadrupole coupling and nuclear spin-rotation coupling have been observed. A Dunham-type analysis has produced unusually large Born-Oppenheimer breakdown parameters, which are interpreted in terms of the electronic structures of the molecules.     

Pulsed EPR studies of polycrystalline cesium hexamethyl hexacyclen sodide

The electron spin echo envelope modulation (ESEEM) technique of pulsed EPR spectroscopy has been used to measure weak¹³³Cs hyperfine couplings to trapped electrons in polycrystalline cesium hexamethyl hexacyclen sodide. Two magnetically distinct groups of weakly coupled¹³³Cs nuclei were found — one with an isotropic electron-nuclear hyperfine (Fermi contact) coupling of 0.34 MHz and the other with a contact coupling less than 0.1 MHz. Analysis of these data, by computer simulation, shows that the number of Cs nuclei that give rise to these interactions and their distance from the paramagnetic center is consistent with the hypothesis that the trapped electrons occupy vacant anion sites. The results indicate that the spread of unpaired electron spin density, along the axis formed by the “contact ion pair,” may be greater than that in the plane perpendicular to this axis.     

Non-empirical calculation of the electronic energy levels of the BF3 + ion. Interpretation of the photoelectron spectrum of BF3

There is a strong interaction between Na⁺ ions and the stable nitroxide radical 2,2,6,6-tetramethyl piperidinyl oxide (TMPN) in THF solution. The paramagnetic shift of the ²³Na resonance indicates that positive unpaired spin density is present at the sodium nucleus. The temperature dependence of the contact shift shows that complex formation is entropy-driven, since the TMPN - Na⁺ complex is endothermic by 8 ± 0·4 kJ mol^-1. Ab initio calculations, performed on a model system, indicate that attachment of the sodium cation to oxygen or to nitrogen leads to conformations whose energies are rather similar; only II(N) geometries are characterized by positive spin densities on sodium, as found experimentally. The longitudinal and transverse relaxation rates also point, from their relative magnitudes, to a predominant contribution from scalar I · S coupling, confirming a considerable degree of spin density transfer from the radical to the sodium nucleus.     

Improved Estimation of CSA–Dipolar Coupling Cross-Correlation Rates from Laboratory-Frame Relaxation Experiments

We have investigated the underlying assumptions in estimating cross-correlation rates between chemical shift anisotropy (CSA) and dipolar coupling mechanisms in a scalar-coupled two-spin IS system, from laboratory frame relaxation experiments. It has been shown that for an arbitrary relaxation delay, the difference in relaxation rates of the individual components of an in-phase (or antiphase) doublet is not related to the CSA–dipolar coupling cross-correlation rate in a simple way. This is especially true in the case where the difference in the decay rates of the in-phase and antiphase terms of the density matrix becomes comparable to the magnitude of the scalar coupling between the two spins. Improved means of extracting cross-correlation rates in these cases are presented.     

Zeeman relaxation of CaF in low-temperature collisions with helium

The collision-induced Zeeman relaxation rate for collisions of CaF X2Sigma(v(')=0) with 3He is measured to be Gamma(Z)=(7.7+5.4/-2.5)x10(-15) cm(3)/s at 2 K. This rate is a direct measurement of the influence of spin-rotation coupling on Zeeman relaxation in the first rotational level of CaF. The relationship of this rate to known molecular constants is consistent with recent theory of cold molecular collisions and outlines the (2)Sigma molecules conducive to magnetic trapping.     

Double electron-electron resonance in electron spin echo: Conformations of spin-labeled poly-4-vinilpyridine in glassy solutions

Double electron-electron resonance in electron spin echo has been used to study the glassy solutions of poly-4-vinylpyridine doped by nitroxyl radicals frozen in liquid nitrogen. The phase relaxation of spin labels due to spin-spin interaction of unpaired electrons has been studied. The intramolecular and intermolecular contributions of the dipole-dipole interaction of spin labels into relaxation process have been separated. It has been established that both the intramolecular and intermolecular spin-spin interaction of spin labels lead to the dependence of echo signal on timeT of the exp (?aT ^q ) type. It is shown that for the intramolecular interaction the experimentalq value is 0.3, for the intermolecular one it is 2. The assumption has been made of the linear structure of polymeric molecules due to the presence of a sufficiently high density of an electric charge on polymeric molecules.     

Depolarization of luminescence of polyatomic molecules in the gas phase as a method of determining the efficiency of collisional transfer of angular momentum

The theory of collisional depolarization of luminescence of extended polyatomic molecules in rarefiedgases is considered. The interrelation between the frequency of collisions, the relaxation time of the angular momentum, and the cross section of the luminescence depolarization is established, and the dependence of these parameters on the efficiency of an abrupt change in the angular momentum is calculated. The use of the theory of collisions of solids in the Enskog approximation made it possible to take into account the effect of the shape and mass of colliding molecules on the degree of depolarization. It is established that, in terms of this theory, there exists a limiting efficiency of an abrupt change in the angular momentum, which, however, does not attain the value proposed in the model of strong collisions (Jdiffusion). The dependence of the depolarization of luminescence of 1,4-di-(2-5-p-tolyloxazolyl) benzene molecules on the concentration of a buffer gas (argon) is measured. It is found that about five collisions with Ar atoms are required for randomization of the angular momentum of these molecules.     

An NMR study of the origin of dioxygen-induced spin-lattice relaxation enhancement and chemical shift perturbation

Due to its depth-dependent solubility, oxygen exerts paramagnetic effects which become progressively greater toward the hydrophobic interior of micelles, and lipid bilayer membranes. This paramagnetic gradient, which is manifested as contact shift perturbations (19F and 13C NMR) and spin-lattice relaxation enhancement (19F and 1H NMR), has been shown to be useful for precisely determining immersion depth, membrane protein secondary structure, and overall topology of membrane proteins. We have investigated the influence of oxygen on 19F and 13C NMR spectra and spin-lattice relaxation rates of a semiperfluorinated detergent, (8,8,8)-trifluoro (3,3,4,4,5,5,6,6,7,7)-difluoro octylmaltoside (TFOM) in a model membrane system, to determine the dominant paramagnetic spin-lattice relaxation and shift-perturbation mechanism. Based on the ratio of paramagnetic spin-lattice relaxation rates of 19F and directly bonded 13C nuclei, we conclude that the dominant relaxation mechanism must be dipolar. Furthermore, the temperature dependence of oxygen-induced chemical shift perturbations in 9F NMR spectra suggests a contact interaction is the dominant shift mechanism. The respective hyperfine coupling constants for 19F and 13C nuclei can then be estimated from the contact shifts <(deltav/v0)19F> and <(deltav/v0)13C>, allowing us to estimate the relative contribution of scalar and dipolar relaxation to 19F and 13C nuclei. We conclude that the contribution to spin-lattice relaxation from the oxygen induced paramagnetic scalar mechanism is negligible.     

Proton Detection of Heteronuclear Dipolar Couplings

A method is proposed for the calculation of heteronuclear dipolar coupling between two 1/2 nuclei, X and Y, by measuring the spin-lattice relaxation rates of the abundant Y nucleus and of the satellite peaks (¹H, ³¹P, ¹⁹F) due to the scalar coupling of Y with the less abundant X nucleus. The ¹H-¹³C dipolar interaction has been evaluated from the proton spin-lattice relaxation rates of tyrosine in water solution and the effective correlation times of the aromatic moiety have been calculated.     

A method for constructing radial wave packets with application to target distortion in electron-atom collisions

It has been shown that an analysis of radial stationary state wave functions of a particle in terms of their loops leads to such continuous, single-valued and finite functions which represent a practically convenient form of the radial wave packets of that particle at various positions. The radial wave packets have been used to investigate target distortion in electron-atom collisions. The distortion of the target is defined in terms of quantum-mechanical probabilities given by the wave packets. A closed expression which depends upon the position of the colliding electron, is obtained for the potential energy of the target in the field of the colliding electron.     

Correlations in ballistic processes

We investigate a class of reaction processes in which particles move ballistically and react upon colliding. We show that correlations between velocities of colliding particles play a crucial role in the long time behavior. In the reaction-controlled limit when particles undergo mostly elastic collisions and therefore are always near equilibrium, the correlations are accounted analytically. For ballistic aggregation, for instance, the density decays as n approximately t(-xi) with xi=2d/(d+3) in the reaction-controlled limit in d dimensions, in contrast with the well-known mean-field prediction xi=2d/(d+2).     

Influence of momentum-dependent interactions on balance energy and mass dependence⋆

We aim to understand the role of momentum-dependent interactions in transverse flow as well as in its disappearance. For the present study, central collisions involving masses between 24 and 394 are considered. We find that the momentum-dependent interactions have different impact in lighter colliding nuclei compared to heavier colliding nuclei. In lighter nuclei, the contribution of the mean field towards flow is smaller compared to heavier nuclei where binary nucleon-nucleon collisions dominate the scene. The inclusion of momentum-dependent interactions also explains the energy of the vanishing flow in the ¹²C + ¹²C reaction which otherwise was not possible with the static hard equation of state. An excellent agreement of our theoretical attempt is found for balance energy with experimental data throughout the periodic table.     

Electron Energy Distribution Functions in RF Molecular Plasmas: The Role of Second Kind Collisions

Electron energy distribution functions in rf molecular plasmas have been calculated by solving the time dependent Boltzmann equation in the presence as well as the absence of vibrationally and electronically excited molecules and thus of first kind and second kind (superelastic) collisions with them. The results, which refer to a model plasma composed by three components (the ground state, a lumped vibrational state and a lumped electronic state), show that these collisions with vibrationally and electronically excited molecules strongly affect the modulation of the electron energy distribution function and related quantities.     

He^＋＋H^—和Li^＋＋D^—碰撞的电荷转移截面计算

用多通道Ｌａｎｄａｕ－Ｚｅｎｅｒ方法计算了Ｈｅ＋＋Ｈ－和Ｌｉ＋＋Ｄ－低能碰撞过程中电荷转移截面，碰撞体系的初态与末态间的耦合矩阵元由渐近方法得到。计算结果与最近的实验结果进行了比较     

Collisional stability of fermionic Feshbach molecules

Using a Feshbach resonance, we create ultracold fermionic molecules starting from a Bose-Fermi atom gas mixture. The resulting mixture of atoms and weakly bound molecules provides a rich system for studying few-body collisions because of the variety of atomic collision partners for molecules; either bosonic, fermionic, or distinguishable atoms. Inelastic loss of the molecules near the Feshbach resonance is dramatically affected by the quantum statistics of the colliding particles and the scattering length. In particular, we observe a molecule lifetime as long as 100 ms near the Feshbach resonance.     

Energy losses of fast heavy structure ions in multiple collisions with diatomic molecules

The nonperturbative calculations of the effects of multiple collisions and the orientation of the molecule axis with respect to the projectile motion direction in the energy losses of fast heavy highly charged structure ions colliding with diatomic molecules have been performed with allowance for various excitations and the ionization of both the projectile and target. It has been shown that the effects of multiple collisions gives rise to a significant difference between the energy losses at the parallel and perpendicular orientations of the target; this effect is insignificant for chaotic orientation. Conclusions for the cross sections for the stripping of hydrogen-like ions are similar.     

Energy losses of fast heavy multiply charged structural ions in collisions with complex atoms

A nonperturbatve theory of energy losses of fast heavy multiply charged structural ions in collisions with neutral complex atoms is elaborated with allowance for simultaneous excitations of ionic and atomic electron shells. Formulas for the effective deceleration that are similar to the well-known Bethe-Bloch formulas are derived. By way of example, the energy lost by partially stripped U ^q+ ions (10 ≤ q ≤ 70) colliding with argon atoms and also the energy lost by Au, Pb, and Bi ions colliding with various targets are calculated. The results of calculation are compared with experimental data.