Ionization of hydrogen and helium atoms by highly charged fast ions in collisions with small momentum transfer

Ionization of hydrogen and helium atoms is studied for the case of “soft” collisions with highly charged fast ions with v≲Z≪v² and v≫v ₀, where Z is the ion charge, v is the collision velocity, and v ₀∼1 is the characteristic velocity of the electron in the ground state of the atom. Analytical expressions are derived for the singly and doubly differential cross section for ionization of a hydrogen atom accompanied by the ejection of a slow electron v _e≲v ₀, where v _e is the velocity of the ejected electron with respect to the recoil ion). The results are generalized to the case of single ionization of helium. It is shown that soft collisions provide the main contribution to the hydrogen ionization cross section and for all practical purposes determine the cross section for single ionization of helium. The asymmetry in the angular distribution of the ejected slow electrons and the properties of momentum exchange in such collisions are discussed. Finally, a formula for the cross section for single ionization of helium is proposed. Zh. éksp. Teor. Fiz. 112, 1966–1977 (December 1997)     

A translational energy spectrometer to probe interatomic potentials: Dissociation dynamics of CO2 + ions

A new ion translational energy spectrometer has been developed to carry out low-energy, gas-phase ion-molecule collision experiments which aim to probe molecular potential energy surfaces. The collisional technique employed relates small changes in the kinetic energy of a projectile ion after it has undergone collision with a static neutral atom/molecule to changes in the overall potential energy of the collision system; information can be furnished about the interaction potential between the projectile and the target. First measurements are reported of a high resolution target excitation spectrum obtained in 1.8 keV collisions of H₂ ⁺ ions with N₂. New results pertaining to collision-induced dissociation of CO₂ ⁺ ions are presented and discussed in terms of potential functions of low-lying electronic states of the molecular ion.     

Potential curves from continuous spectra: He2 X 1Σ g + and A 1Σ u +

Continuous electronic spectra of diatomic molecules can often be related to the associated potential curves. It is demonstrated that the local nature of continuous spectra may greatly facilitate inversion of the spectra to obtain ground and excited state potential curves. All of the observed continuous spectra related to transitions between the X and A states of the helium diatomic molecule are re-examined with the goal of determining accurate potential curves for the two states. It is shown that the excited state dissociation energy is 2·50±0·03 eV and that the MDD-1 potential proposed by Bruch and McGee is the preferred choice to represent the ground state interaction. Also, the mean cross section at 300 K for the destruction of a 2¹ S helium atom by collision-induced emission is evaluated and found to be 2·8 × 10^-20 cm² in agreement with the measurements of Phelps.     

Quantum-dynamical study of the translational-vibrational energy transfer in the collinear collisions of atoms with triatomic molecules

A quantum-dynamical method is described for investigating the translational-vibrational energy transfer that occurs in the collinear collision of an atom with a linear triatomic molecule. The technique is applied to the computation of vibrational transition probabilities for the collinear collisions of helium atoms with CO₂, OCS and HCN over a range of energies. Realistic potentials are used for the triatomic molecules while simple exponential or Morse potentials are used to describe the helium-molecule interaction. The effects of varying the atomic masses and the potential function parameters are examined. It is found, that the symmetric stretch vibrational modes of CO₂, OCS and HCN are preferentially excited (or relaxed), by collision with the atom, over the asymmetric stretch modes.     

Encapsulation of methane molecules into carbon nanotubes

Methane gas (CH₄) is a chemical compound comprising a carbon atom surrounded by four hydrogen atoms, and carbon nanotubes have been proposed as possible molecular containers for the storage of such gases. In this paper, we investigate the interaction energy between a CH₄ molecule and a carbon nanotube using two different models for the CH₄ molecule, the first discrete and the second continuous. In the first model, we consider the total interaction as the sum of the individual interactions between each atom of the molecule and the nanotube. We first determine the interaction energy by assuming that the carbon atom and one of the hydrogen atoms lie on the axis of the tube with the other three hydrogen atoms offset from the axis. Symmetry is assumed with regard to the arrangement of the three hydrogen atoms surrounding the carbon atom on the axis. We then rotate the atomic position into 100 discrete orientations and determine the average interaction energy from all orientations. In the second model, we approximate the CH₄ molecule by assuming that the four hydrogen atoms are smeared over a spherical surface of a certain radius with the carbon atom located at the center of the sphere. The total interaction energy between the CH₄ molecule and the carbon nanotube for this model is calculated as the sum of the individual interaction energies between both the carbon atom and the spherical surface and the carbon nanotube. These models are analyzed to determine the dimensions of the particular nanotubes which will readily suck-up CH₄ molecules. Our results determine the minimum and maximum interaction energies required for CH₄ encapsulation in different tube sizes, and establish the second model of the CH₄ molecule as a simple and elegant model which might be exploited for other problems.     

Controlled synthesis and analysis of He–H+3 in a 3.7 K ion trap

Complexes of the triatomic hydrogen ion with helium were synthesised in a low-temperature 22-pole rf ion trap at He number densities of up to 10¹⁶ cm^?3. Absolute ternary rate coefficients for sequentially attaching He atoms have been determined from the growth of complexes with increasing storage time. The number of helium-tagged ions is significantly reduced when increasing the nominal temperature from 4 to 25 K. Competition between attachment and dissociation via collisions leads to stationary He_n–H⁺₃ (n up to 9) distributions. State-specific excitation of the trapped H⁺₃ ions via IR transitions significantly reduces the formation of complexes. Tuning the laser to Δv₂ = 1 transitions in the range of 2726 cm^?1 leads to LIICG lines, i.e., to spectra caused by laser-induced inhibition of complex growth. In addition, almost 100 lines have been found between 2700 and 2765 cm^?1, which are attributed to laser-induced dissociation of the in situ formed He–H⁺₃ complex ions. These lines are not yet assigned; however, their absorption strength, statistics and predissociation lifetimes provide interesting information on both the stable complexes as well as on scattering resonances in low-energy H⁺₃+He collisions. New calculations of the potential energy surface will help to analyse the dissociation spectrum. There are some indications that para-H⁺₃ is enriched under the conditions of the present experiment.     

Calculation of potential energy curves for Rb2 including relativistic effects

All-electron relativistic calculations have been performed on the Rb₂ molecule. The molecular orbitals are optimized within a spin-free no-pair Hamiltonian formalism and spin-orbit coupling is treated using quasi-degenerate perturbation theory. Potential curves of the ground state and several excited states are calculated, and the spectroscopic constants T _e, D _e, R _e and ω_e are in good agreement with experimental values. The spin-orbit splittings at the 5p and 6p asymptotic limits are found to be underestimated by about 30%. Large perturbations in the spectra from the 1¹Σ⁺ _u(A) state are predicted due to an avoided crossing with a 1 ³Π_ub state caused by spin-orbit interaction. The predissociation dynamics of the 2 ¹Π_uC and 3 ¹Π_uD states is discussed. The calculations support the observation that a (1) ³ Δ_u state causes the fast predissociation of the ^{3 1}Π_uD state but rule out the (2)³Σ⁺ _u state as causing the slow predissociation at the lower part of the 3 ¹Π_uD potential energy curve.     

Transition probabilities for two-photon H(1s–2s) and He(11s–21s) transitions: A partial-closure approach

Transition amplitudes and transition probabilities for the two-photon 1s–2s transition in the hydrogen atom and 1¹ s–2¹ s transition in helium atom have been calculated using a partial-closure approach. The dominant term is calculated exactly and the remaining sum over intermediate states is calculated using a mean excitation energy. Our value of the transition amplitudes agree within 2% with the exact results for the hydrogen case. Our value of the transition probability for hydrogen is 8.50 s⁻¹ which is in good accord with its known value 8.226 s⁻¹. For helium, the photon energy distribution of the metastable 2¹ s state is in good agreement with the accurate values. The corresponding transition probability is 53.7 s⁻¹ which is in good agreement with the accurate value 51.3 s⁻¹.     

Modifications in high energy higher order Born approximation

A systematic study is made to find out the differential scattering cross-section in the case of electron-atom collisions. The first and the second Born terms ofO(1/k _i ) are calculated in the framework of Yates high energy higher order Born approximation. The second Born term ofO(1/k _i ² ) is calculated using the second order Wallace term, the third term is calculated using the Glauber-eikonal series of Yates. The method is applied to the elastic scattering of electrons by atomic hydrogen in the energy range 100–400 eV and by helium for energies 200 eV and 400 eV. Comparison is made with other theoretical results and the experimental data.     

乙醚团簇的激光电离质谱及从头计算

应用激光多光子电离质谱与超声脉冲分子束技术研究了乙醚团簇，实验中观测到乙醚的碎片离子以及强度较小的(E)H⁺，(E)^＋₂和(E)₂H⁺(E代表CH₃CH₂OCH₂CH₃)，没有发现更大尺寸的团簇离子.结合从头计算理论，在B3LYP/6-311++G(d,p 关键词： 乙醚团簇 偶极-偶极相互作用 从头计算     

Adsorption of helium on isolated C60 and C70 anions

Adsorption of helium on free, negatively charged fullerenes is studied in this work. Helium nanodroplets have been doped with fullerenes and ionised by electron attachment. For suitable experimental conditions, C^?₆₀ and C^?₇₀ anions are found to be complexed with a large number of helium atoms. Prominent anomalies in the ion abundances indicate the high stability of the commensurate 1×1 phase in which all hollow adsorption sites are occupied by one atom each. The adsorption energy for an additional helium atom is about 40% less than for atoms in the commensurate layer, similar to our previous findings for fullerene cations and in agreement with theoretical dissociation energies. Similarly, an anomaly in the adsorption energy occurs when 60 helium atoms are attached to C^?₆₀ or 65 to C^?₇₀. For C₆₀, the anomaly coincides with the one observed for cationic complexes but for C₇₀ it does not. Implications of these features are discussed in light of several theoretical studies of neutral and positively charged helium–fullerene complexes.     

Hydration-induced conformational changes in protonated 2,4-pentanedione in the gas phase

Starting with H⁺[CH₃C(O)CH₂C(O)CH₃] (denoted H⁺PD), the protonated diketone-water clusters H⁺PD(H₂O) _n (n = 1–3) have been characterized by density functional theory calculations in combination with vibrational predissociation spectroscopy to explore the conformational changes of a protonated bifunctional ion solvated by water in the gas phase. Theoretical calculations for H⁺PD revealed that the ion contains an intramolecular hydrogen bond (IHB), with two oxygen atoms bridged by the extra proton in an O—H⁺ … O form. Attachment of one water molecule to it readily ruptures this IHB, replacing the H⁺ by the H₃O⁺ moiety. Further replacement of the IHB by two water molecules occurs at n = 2 and the ?C(O)CH₂C(O)- chain is fully opened (or unfolded) after transfer of the extra proton to the water trimer at n = 3. To verify the computational findings, infrared spectroscopic measurements were performed using a vibrational predissociation ion trap spectrometer to identify cluster isomers from the signatures of hydrogen bonded and non-hydrogen bonded OH stretching spectra of H⁺PD(H₂O)_2,3 produced in a corona discharge supersonic expansion. Besides open form isomers, evidence for the formation of water-bridged structures has been found for H⁺PD(H₂O)₃ at an estimated temperature of 200 K. A detailed illustration of the unfolding steps as well as the energy profiles for the evolution of a two-water bridge isomer from the protonated H⁺PD monomer are analysed pictorially (including both stable intermediates and transition states) in the present investigation.     

Ramsauer–Townsend Effect in Solid Hydrogen

The TRIUMF E742 experiment has measured the energy dependence of the scattering cross-sections of muonic deuterium and tritium on hydrogen molecules for collisions in the energy range 0.1–45 eV. The experimental setup permits the creation of muonic atom (μd or μt) beams. The multilayered target system gives the possibility to choose the type of interactions to study and to isolate a particular interaction. The scattering of μd or μt beams on H₂ is analyzed via the muon transfer reaction to neon. The time-of-flight method is used to measure the scattering cross section as a function of the energy of the muonic atom beam. The results are compared, using Monte Carlo simulations, with theoretical calculations which have been recently performed with high accuracy. This revised version was published online in August 2006 with corrections to the Cover Date.     

Observation of the Molecular Quenching of μp(2S) Atoms

Kinetic energy distributions of muonic hydrogen atoms μp(1S) have been obtained by means of a time-of-flight technique for hydrogen gas pressures between 4 and 64 hPa. A high energy component of ∼900 eV observed in the data is interpreted as the signature of long-lived μp(2S) atoms, which are quenched in a non-radiative process leading to the observed high energy: the collision of a thermalized μp(2S) atom with a hydrogen molecule H₂ results in the resonant formation of a {[(ppμ)⁺]^*pee}^* molecule. Then the (ppμ)⁺ complex undergoes Coulomb de-excitation and the ∼1.9 keV excitation energy is shared between a μp(1S) atom and one proton. The preliminary analysis of the time spectra gives a long-lived μp(2S) population of ∼1% of all stopped muons, and a quenching rate of ∼4⋅10¹¹ s⁻¹. This revised version was published online in August 2006 with corrections to the Cover Date.     

Helium transport along lattice channels in crystalline quartz

The problem of He atom movement through channels of the quartz crystalline lattice is investigated. Providing the diameters of the atom and of the channel are of similar size the atom interacts with neighbor constituents of the wall. The conservation of momentum law in local form applied to the ‘helium-constituent’ interaction allows reduction of the problem to a one-dimensional one, which is similar to the movement of a dislocation in the Frenkel-Kontorova (FK) model. Within the framework of this model the activation energy for ‘helium+neighbor constituents’ is expressed by the shear modulus for the channel-forming material and the He polarizability. A metastable helium atom in the triplet state (2 ³S₁) is able to penetrate through the channel. In contrast, helium atoms in the singlet states, both ground state (1 ¹S₀) and metastable (2 ¹S₀), cannot penetrate.     

Accumulation and annealing of implantation damage in a-Si:H

Hydrogenated amorphous silicon (a-Si:H) films have been irradiated with H⁺, B⁺, P⁺, and Ar⁺ ion beams. The accumulation and the annealing of irradiation-induced defects has been investigated through a series of electronic transport and PDS measurements. We find that for all projectiles damage accumulation is dominated by atomic displacement collisions with the damage saturating for energy transfers in excess of about 10 eV/target atom. Annealing at elevated temperatures causes the conductivity of doped and irradiated a-Si:H films to increase according to stretched exponential decay curves. All annealing parameters derivable from such fits scale with the energy originally dissipated into atomic displacement collisions. For energy transfers up to 10 eV/target atom the activation energy for annealing increases up to a saturation value and, at the same time, an increasing fraction of the irradiation-induced defects becomes stable against annealing at moderate temperatures (T _a<250° C). We discuss these results with respect to damage accumulation data in crystalline silicon (c-Si) and with regard to the annealing of metastable defects in a-Si:H.     

Atomistics of helium diffusion in copper and tungsten

Using previously determined interatomic potentials, the activation energy for migration of a single substitutional helium atom in copper and tungsten has been determined. The mechanism of migration involves the jump of the helium atom out of the vacancy concurrent with the jump of a host atom into that vacancy. The helium then occupies the vacant site created by the jumping host atom, resulting in a substitutional helium at a distance of √2 r ₀ (√3r ₀) from its original site in copper (tungsten). The rate-limiting step in the process is found to be the jump of the helium out of the vacancy, the activation energy for which is 2.15 eV in copper and 4.69 eV in tungsten.     

纳秒激光诱导铜等离子体中原子激发态5s′~4D_(7/2)的瞬态特性研究

利用时间分辨光谱技术,研究了激光诱导Cu等离子体中激发态5s′4D7/2的形成及其辐射跃迁的瞬态特性.结果表明:在激发态5s′4D7/2原子的制备过程中,电子离子复合、粒子间碰撞机理在不同时刻分别起主导作用.激光峰值到达金属表面后500ns期间,粒子间的剧烈碰撞作用使得激发态5s′4D7/2主要通过向低能态4p′4F9o/2跃迁来转移能量.500ns以后,激发态5s′4D7/2通过以相同的概率辐射CuI465.11nm和CuI529.25nm特征谱线向低能态4p′4F9o/2和4p′4D7o/2转移能量.     

The I2(B) predissociation by solving an inverse atoms-in-molecule problem

The valence electronic states of the iodine molecule are analysed by means of a simple atoms-in-molecule model which accounts for the lowest ²P states of iodine atoms and approximates the spin-orbit interaction by its atomic part. For this model, an inverse problem is solved, i.e. non-relativistic potential energy curves and diabatic couplings are determined by a least-squares fit to known relativistic potential energy curves. The resulting adiabatic wave functions are used to calculate the electronic matrix elements responsible for natural, hyperfine and magnetic predissociation of the iodine molecule in the B0⁺ _u: state. The results are in reasonable agreement with experimental data, being stable enough with respect to the variation of input relativistic potentials. They also indicate the importance of diabatic couplings between the non-relativistic states of the same symmetry.