Electronic recoil effects in high-energy photoelectron spectroscopy

It is shown that the recoil energy imparted to the residual ion by the outgoing fast photoelectron leads to noticeable modifications of X-ray excited photoelectron spectra of molecules containing light atoms. The vibrational band envelopes may differ considerably from those predicted by the Franck-Condon principle. Al Kα excited valence electron bands are shown to exhibit, in addition to the translational recoil energy of the molecule, energy shifts of up to several tenth of an eV due to recoil-induced vibrational and rotational excitation. This effect has to be kept in mind when ionization potentials are determined from ESCA spectra. The recoil-induced vibrational and rotational excitation depends on the orbital quantum numbers of the ionized electron. Simple formulae for the shift of the centroid and the broadening of the band due to recoil effects are given for the special case of diatomic molecules.     

Optical Emission of Molecular Hydrogen in a Recombining Hydrogen Plasma

We observed optical emission of molecular hydrogen in a recombining hydrogen plasma with an electron temperature of 0.1 eV and an electron density of 3 × 10¹²cm^–3. The optical emission intensities of molecular hydrogen in the recombining plasma were roughly 10%–45% of those in an ionizing plasma with an electron temperature of 4 eV. The ratio was greater for a transition line originated from an excited state with a larger vibrational quantum number. Because of the low electron temperature of 0.1 eV, the production processes of excited states are not considered electron impact excitation in the recombining plasma. Possible recombination processes are discussed which produce excited states of molecular hydrogen in the recombining plasma (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Analysis of extraterrestrial particles using monochromated electron energy-loss spectroscopy

A monochromated (scanning) transmission electron microscope was used to analyze individual sub-micron grains within interplanetary dust particles (IDP). Using low-loss and core-loss electron energy-loss spectroscopy, we analyzed fluid and gas inclusions within vesiculated alumosilicate grains. It is shown that nanometer-sized vesicles contain predominantly molecular oxygen (O(2)) beside a small fraction of H(2)O. Low-loss spectra reveal the Schumann-Runge continuum peaking at 8.6 eV and absorption bands reflecting vibrational excitation states of O(2) molecules between the first (12.1 eV) and second (16.1 eV) ionization energy. The presence of oxygen gas is supported by the corresponding oxygen K-edge fine structure. The valence state of Fe in iron-oxide within the IDP was also studied. Low-loss spectra provide qualitative information about the oxidation state of iron consistent with the Fe(2+)/Fe(3+) ratio quantitatively derived from the Fe L(2,3) edge.     

Vibrational-rotational energy transfer in H2-H2 collisions: III. Ortho-ortho collisions

A recently proposed[1999, J. chem. Phys., 111, 2401 and 1999, Chem. Phys. Lett., 312, 530] new semi-classical decoupling procedure for rotational projection states in ro-vibrationally inelastic atom-diatom and diatom-diatom collisions is applied to inelastic collisions in molecular hydrogen. The role of initial rotational excitation of both collision partners in the ro-vibrational transitions, attached to the vibrational (10 -> 00) transition in ortho-H₂, is analysed in detail. The computed vibrational self-relaxation rate constant for ortho-H₂ (as earlier for para-H₂, too) is in good quantitative agreement (within a factor of 2) with experimental data over the whole experimentally investigated temperature range, 50-3000 K. This also indicates that the more detailed (non-measured) rate constants for ro-vibrational state-to-state transitions in molecular hydrogen, calculated by our new model, are sufficiently accurate for astrophysical applications.     

Collisional and radiative processes with participation of highly excited states of atoms and molecules

A number of processes in which highly excited states of atoms and molecules participate are investigated. These processes are of interest for the kinetics of a low-temperature plasma, for atomic and molecular spectroscopy, and for astrophysics. A quasiclassical theory is developed for transitions between Rydberg states with change of the principal quantum number, and also for the processes of direct and associative ionization of highly excited atoms, which result from collisions between a neutral particle and its atomic core. The state of the inner electrons of a quasimolecular (molecular) ion is not altered by transitions of the outer electrons. Specific calculations are carried out for the case of the collision of hydrogen H(n) with helium He (1s²) atoms. It is shown that the cross sections and the rate constants of these processes are determined in this case by the mechanism investigated in the paper, and not by scattering of the Rydberg electron by the neutral particle. The cross sections for dipole excitation and dissociation of molecular ions from high vibrational energy levels by electron impact is calculated in the Born-Coulomb approximation. The cross sections and the rates of dissociative and three-particle attachment of electrons to ions are determined. The processes of autoionization and autodissociation decay of Rydberg states of vibrationally excited molecules are determined. Also investigated are radiative transitions near the dissociation limit of diatomic molecular ions and neutral molecules, viz., photodissociation and radiative decay of high vibrational levels, and photodissociation and translational (inverse-bremsstrahlung) absorption in collision of atomic particles.Translated from Trudy Ordena Lenina Fizicheskogo Instituta im. P. Lebedeva AN SSSR, Vol. 145, pp. 80–130, 1984.     

Triplet-triplet transfer of electronic energy upon nonequilibrium vibrational excitation of triplet molecules

The specific features of the triplet-triplet (T-T) transfer of electronic excitation energy in a gas phase upon nonequilibrium vibrational excitation of the triplet molecules of a donor were studied for an anthraquinone-diacetyl donor-acceptor pair using the time-resolved slow fluoresence of anthraquinone and sensitized phosphorescence of diacetyl. It is shown that in the gas phase, which allows regular control of the number of collisions, competition between the processes of T-T transfer and intermolecular vibrational relaxation is observed for nanosecond time resolution. The T-T transfer rate for the molecular system investigated exceeded the rate of intermolecular vibrational relaxation k_V in the triplet state T₁ of the donor. The effectiveness of the T-T transfer of energy by vibrationally excited molecules turned out to be higher than the effectiveness of transfer by thermalized ones, but even the highest of them was much less than unity. An increase in the equilibrium temperature of vapors led to a decrease in the effectiveness of transfer for both vibrationally excited and thermalized triplet molecules, thus indicating the importance of the collisional complex in the intermolecular process studied. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 474–479, July–August, 2000.     

Schwingungsanregung von H2-Molekülen durch Zentralstoß mit Li+-Ionen

An apparatus is described for measuring the inelastic differential cross section for vibrational excitation in collisions of diatomic molecules with monoenergetic ions at laboratory energies between 10 and 50 eV. The method consists of measuring the time of flight of single ions with a time amplitude converter and displaying the results on a 100 channel pulse height analyzer. From the shift in the time of flight relative to that expected for elastic scattering the final state of the molecule excited in a single collision is identified. By studying only central collisions with almost zero impact parameter rotational excitation is strongly suppressed. Measured times of flight after collisions of monoenergetic Li⁺ ions with H₂ show that with increasing energy the most probable vibrational quantum jump increases from 0→1 to 0→2,0→3 etc. Contrary to the usual assumption of a small steric factor for vibrational excitation the results show that the inelastic cross section is larger than the elastic cross section. Using reported potential parameters the energy dependence of the most probable excited state is compared with the calculations of Secrest and Johnson for a one-dimensional collinear collision. The satisfactory agreement suggests that the steric factor is close to 1. From measurements at different scattering angles at 10 eV the integral inelastic cross section is found to be about 0.2 Ų corresponding to a differential cross section of 0.4 Ų/sr. Measured values of integral and differential total cross sections for Li⁺-He andLi⁺-H₂ are reported and compared with theory. Direct dissociation of D₂ by Li⁺ in the energy range from 25 to 55 eV was not observed, yielding an upper limit for the cross section of 4 · 10^?4 Ų/sr.     

弱电离大气等离子体电子碰撞能量损失的理论研究

在前期计算电子能量分布函数的基础上, 求出弱电离大气等离子体中各碰撞反应过程的电子能量损失. 由于在弹性碰撞中电子-重粒子能量交换很少, 同时氮气、氧气分子又有很多能量阈值较低的转动、振动能级存在, 因此在大气等离子体中弹性碰撞电子能量损失所占份额很小(直流电场下小于6%). 研究发现, 弱电离大气等离子体中在不同能量区间占主导的能量损失过程不同. 随着有效电子温度(或约化场强)增加, 占主导的电子能量损失过程依次为转动激发、振动激发、电子态激发、碰撞电离、加速电离产生的二次电子. 在约化场强E/N=1350 Td (或有效电子温度为14 eV)附近, 平均电离一个电子所需的能量最小, 约为57 eV. 因此可以根据不同的需求调节电场强度, 从而达到较高的能量利用率. 关键词： 弱电离大气等离子体 碰撞反应过程 电子能量损失     

An improved kinetic theory approach for calculating the thermal conductivity of polyatomic gases

A new kinetic theory approach for calculating the thermal conductivity of a dilute polyatomic gas from the intermolecular pair potential is presented. The contributions due to internal degrees of freedom have been separated into a classical rotational and a quantum-mechanical vibrational part. Assuming that the vibrational states of the molecules do not significantly influence the collision trajectories, and that vibrationally inelastic and vibrationally resonant collisions are rare, we have obtained a simple self-diffusion mechanism for the vibrational contribution to the thermal conductivity. For non-polar gases like methane or nitrogen, the new approach yields thermal conductivity values that are very close to those obtained with the previously used kinetic theory approach. However, for polar gases like hydrogen sulphide and water vapour, the values obtained with the new scheme are much closer to the most accurate experimental data.     

Electron spin lattice relaxation rates for S = 12 molecular species in glassy matrices or magnetically dilute solids at temperatures between 10 and 300 K.

The temperature dependence of X-band electron spin-lattice relaxation between about 10 and 300 K in magnetically dilute solids and up to the softening temperature in glassy solvents was analyzed for three organic radicals and 14 S = 12 transition metal complexes. Contributions from the direct, Raman, local vibrational mode, thermally activated, and Orbach processes were considered. For most samples it was necessary to include more than one process to fit the experimental data. Debye temperatures were between 50 and 135 K. For small molecules the Debye temperature required to fit the relaxation data was higher in 1:1 water:glycerol than in organic solvents. For larger molecules the Debye temperature was less dependent upon solvent and more dependent upon the characteristics of the molecule. The coefficients of the Raman process increased with increasing g anisotropy and decreasing rigidity of the molecule. For the transition metal complexes the data are consistent with major contributions from local modes with energies in the range of 185 to 350 K (130 to 240 cm-1). The coefficient for this contribution increases in the order 3d < 4d transition metal. For C-60 anions there is a major contribution from a thermally activated process with an activation energy of about 240 cm-1. For low-spin hemes the dominant contribution at higher temperatures is from a local mode or thermally activated process with a characteristic energy of about 175 cm-1.     

Studies on vibrational excitation differential cross-sections of low-energy electron scattering from N2 molecule

The vibrational excitation differential cross-sections (DCS) of low-energy electron-N₂ scattering are studied using vibrational close-coupling (VCC) method and vibrational scattering potentials which include static, exchange and polarization contributions. By including the contributions of 18 partial waves, 20 vibrational states, and 16 molecular symmetries (up to Λ=7), the converged vibrational excitation (0↦2, 0↦3, 0↦4) DCS agree well with experimental results. Also obtained are converged vibrational (1↦0, 1↦1, 1↦2, 1↦3) DCS, with the impact energies being those of the main resonant peaks (1.92 eV, 1.90 eV, 1.62 eV, 1.63 eV).     

Vibrationally inelastic scattering of high- n Rydberg H atoms from N2 and O2

The vibrationally inelastic scattering of Rydberg H atoms (n = 30-50) from N2 and O2 at E(coll) = 1.84 eV was studied as a function of laboratory deflection angle. On average, 4 times more vibrational excitation was observed in collisions with O2 than with N2. Vibrational excitation of O2 results largely from collisions in which an electron is briefly transferred from O2 to the proton core, while the Rydberg electron remains a spectator. This provides further evidence that the free electron model applies to low energy collisions involving the ionic core leading to substantial momentum transfer.     

Kinetics of radiation cooling of fullerenes

Emission from fullerene molecules excited by means of electron impact in crossed beams under conditions of single collisions between electrons and C₆₀ molecules in a kinetic energy range E _e from 25 to 100 eV was studied experimentally. Emission spectra in a wavelength range from 300 to 800 nm; the emission excitation functions and the temperature of emitting molecules as a function of E _e were measured with a resolution of 1.6–3.2 nm. The contribution to emission from ionized C ₆₀ ^+* molecules has been determined and data on the emissivity of the C ₆₀ ^+* ion have been obtained. It has been shown that the emission spectra can be well approximated with the spectral distribution of thermal emission from a black body (Planck’s formula), taking into account the lowering of emissivity for a small particle. The emission can be observed starting with electron energy of about 27 eV; the emission excitation function is of a nonresonant form, peaking at an energy of E _e ≈70 eV. As E _e is increased, the temperature of emitting particles rises and reaches its maximum value of 3100–3200 K at E _e ≈47 eV.     

The dissociative excitation of doublet and sextet manganese atom levels in collisions of electrons with manganese dibromide molecules

Inelastic collisions of electrons with manganese dibromide molecules were studied by the method of extended crossing beams. These collisions cause the formation of excited manganese atoms in doublet and sextet states. At an exciting electron energy of 100 eV, 52 dissociative excitation cross sections were measured. At electron energies 0–100 eV, three optical excitation functions were recorded. The ratio between excitation cross sections in electron-molecular and electron-atomic collisions is considered.     

Dissociative excitation of even triplet and quintet levels of the iron atom in collisions of electrons with iron diiodide molecules

The method of extended crossing beams is used to study inelastic collisions of slow electrons with iron dichloride molecules. The dissociative excitation of even triplet and quintet levels of the iron atom at the incident electron energy of 100 eV is examined. The resulting dissociative excitation cross sections are compared to the cross sections of the excitation of FeI in electron-atom collisions.     

Model of a homochiral supramolecular string

The model of a homochiral string (from N-trifluoroacetyl-2-amino-3-methylpentanol-1 molecules) is based on experimental data molecular dynamics simulation results. The resulting model string is a hollow stable helix with characteristics consistent with the available experimental data. It is shown that the main contribution to the formation of the string comes from the dispersion interaction (～0.5 eV) of the homochiral molecules in complementary stacks. In this case, neighboring molecular dipoles are anticollinear, whereas the string is antiferroelectric.     

Rotational state effects in the dissociative recombination of H2+

We have studied the dissociative recombination (DR) of molecular hydrogen ions with slow electrons over a range of collision energies from 0 to 400 meV. By employing a pulsed expansion source for rotational cooling and by exploiting super elastic collisions with near-0-eV electrons in a heavy ion storage ring for vibrational cooling, we observe a highly structured DR cross section, comparable to that reported for HD+. Using para-hydrogen-enriched ion beams, we identify for the first time features in the DR cross sections attributed to nu=0, J=even molecules (para-H2) and nu=0, J=odd (ortho-H2) molecules, separately. Indications are given that para levels have different DR rate coefficients from ortho levels for the first four vibrational levels at near-0-eV collisions.     

Theory of molecule-surface scattering at thermal and hyperthermal energies

A theoretical model of molecule-surface scattering is developed which includes energy and momentum transfers between the surface and projectile for both translational and rotational motions and internal mode excitation for the projectile molecule. The translation and rotation motions are treated in the classical limit, while a quantum treatment for internal vibrational mode excitation is used. The results of calculations are compared with recent high-precision measurements of the scattering of a beam of C(2)H(2) molecules from a clean, ordered LiF(001) surface at energies of up to nearly 1 eV. The calculated results for angular distributions and rotational excitations are in good agreement with experiment.     

含振动能激发Boltzmann模型方程气体动理论统一算法验证与分析

为模拟研究高温高马赫数下多原子气体内能激发对跨流域非平衡流动的影响,将转动能、振动能分别作为气体分子速度分布函数的自变量,把转动能和振动能处理为连续分布的能量模式,将Boltzmann方程的碰撞项分解成弹性碰撞项和非弹性碰撞项,同时将非弹性碰撞按一定松弛速率分解为平动-转动能松弛过程和平动-转动-振动能松弛过程,构造了一类考虑振动能激发的Boltzmann模型方程,并证明了其守恒性和H定理.基于内部能量变量对分布函数无穷积分,引入三个约化速度分布函数,得到一组考虑振动能激发的约化速度分布函数控制方程组,使用离散速度坐标法,基于LU-SGS隐式格式和有限体积法求解离散速度分布函数,建立含振动能激发的气体动理论统一算法.通过开展高稀薄流到连续流圆柱绕流问题统一算法与直接模拟蒙特卡罗法模拟结果对比分析,特别是过渡流区平动、转动、振动非平衡效应对绕流流场与物面力热特性的影响机制,证实了所建立的含振动能激发的Boltzmann模型方程及气体动理论统一算法的准确可靠性.     

Experimental investigation of ultracold atom-molecule collisions

Ultracold collisions between Cs atoms and Cs2 dimers in the electronic ground state are observed in an optically trapped gas of atoms and molecules. The Cs2 molecules are formed in the triplet ground state by cw photoassociation through the outer well of the 0-(g) (P3/2) excited electronic state. Inelastic atom-molecule collisions converting internal excitation into kinetic energy lead to a loss of Cs2 molecules from the dipole trap. Rate coefficients are determined for collisions involving Cs atoms in either the F=3 or F=4 hyperfine ground state, and Cs2 molecules in either highly vibrationally excited states (nu'=32-47) or in low vibrational states (nu'=4-6) of the a3 summation(u)+ triplet ground state. The rate coefficients beta approximately 10(-10) cm3/s are found to be largely independent of the vibrational and rotational excitation indicating unitary limited cross sections.