Studies on the full vibrational energy spectra for some electronic states of diatomic molecular ions XY+

The first accurate studies on the vibrational spectroscopic constants and the corresponding full vibrational energy spectra of some electronic states of diatomic molecular ions XY⁺ were performed using algebraic method(AM). The AM is applied on the X¹Σ⁺ state of BeH⁺, the X²Σ⁺ state of CO⁺, the X²Π_g state of F ₂ ⁺ , the A²Π_u state of O ₂ ⁺ and the X²Σ _g ⁺ state of Li ₂ ⁺ . The results show that AM can generate accurate vibrational spectroscopic constants as well as accurate full vibrational energy spectra by using some accurate experimental vibrational energies, and that the AM vibrational energies are better than other theoretical data. __________ Translated from Chinese Journal of Atomic and Molecular Physics, 2005, 22 (4) (in Chinese)     

Control of branching ratio in the photofragmentation of DCl+ ions: Effect of initial vibrational state

Photofragmentation of DCl⁺ ions alternatively leads to the formation of D⁺ + Cl or Cl⁺ + D in competing reaction channels. The branching ratio of the product yields D⁺/Cl⁺ has been investigated theoretically by numerically solving coupled time dependent Schrödinger equations and experimentally by femtosecond (fs) dissociative ionization of DCl. The theoretical analysis shows that this branching ratio increases step-like at intensities, which characteristically depend on the initial vibrational state for nonresonant multiphoton excitation. In general the threshold decreases with increasing initial vibrational quantum number. Experimental studies exhibit a similar step-like behavior of the D⁺/Cl⁺ branching ratio. Here the intensity at which the step occurs characteristically depends on the chirp of the fs-laser pulses, suggesting that different chirp may lead to intermediate DCl⁺ ions differing in the effective vibrational quantum number.     

Study of spatial characteristics of the incomplete surface discharge in atmospheric-pressure air

Spectra of plasma of the incomplete surface discharge in atmospheric-pressure air were measured. Bands of the systems 2⁺, 1⁺, and 1⁻ of nitrogen were identified. It was shown that periodic excitation at the C ³Π _u nitrogen level results in local equilibrium characterized by a vibrational temperature of 2250 K. For the 1⁺ band system of nitrogen, the structure of rotational transitions was resolved; it was found that the distribution in the 1⁺ band system is significantly nonequilibrium due to the A ³Σ _u ⁺ level metastability. Transverse and longitudinal sections of the plasma band were scanned. It was found that the transverse distribution of the emission intensity has a maximum at a distance of 1 mm from the electrode edge followed by an exponential decay. The plasma band width was ∼5 mm. The longitudinal discharge structure consisted of a system of microchannels (with a characteristic diameter of 0.4 mm) with diffuse overlapping. The average channel density was 10–15 cm⁻¹. It was shown that the spatial distribution of incomplete discharge plasma is characterized by high stability against wide-range variations of discharge electrical characteristics. For example, as the excitation voltage varies within 2–6 kV, the plasma band width changed by no more than 1 mm, and the vibrational temperature varied within 10–12%.     

On the nature of emission bands of self-trapped excitons in solid xenon

The paper presents the analysis of experimental data on the temperature dependence of luminescence spectra of solid xenon. The mechanisms of exciton self-trapping down to quasi-molecular states under different conditions are discussed. A new treatment of spectral distribution of intensity through quasi-molecular luminescence bands is proposed; according to the treatment, at T < 55 K the emission is associated with the transition from the lowest vibrational relaxation excited state ³Σ_u⁺, while at T 60 K from the term ¹Σ_u⁺. Spectral redistribution of intensities in the 60–150 K range is due to an increase in the rate of vibrational relaxation in the state ¹Σ_u⁺ with increasing the crystal temperature.     

Emission spectrum of MgCl molecule in 5030-4380Å

The emission spectrum of diatomic magnesium chloride molecule has been reinvestigated in the region 5030-4380 Å (B ²Σ⁺ —A ²Π transition) at a higher dispersion. The vibrational assignments of the bands are confirmed by observing the vibrational isotope shifts due to isotopes of magnesium and chlorine. Precise values of the vibrational constants are determined for theB ²Σ⁺ state.     

Spectroscopic study of an rf discharge in nitrogen

The absolute populations of the vibrational levels of the B³Πg and C³Π_u states in an rf nitrogen discharge are calculated from the quantum yields of the 1⁺ and 2⁺ systems in the discharge, and the “excitation temperature” of these states is measured. Emission spectroscopic methods are used to determine the vibrational and rotational temperatures of the C³Π_u state, as well as the vibrational temperature of the B³Π_g state. These data are used to estimate the vibrational temperature of the X′∑ _g ⁺ state and the stored energy in the activated nitrogen, and to examine the mechanism by which translational-vibrational degrees of freedom are excited in nitrogen molecules in the discharge.     

The analysis of nitrogen rotational and vibrational bands in a helium microhollow gas discharge

Emission spectroscopy is applied to measure the gas temperature T _g and the vibrational distribution of N₂ (C ³Π_u) and N₂ ⁺(B ²Σ_u ⁺) excited states from a helium microhollow gas discharge (MHGD) at atmospheric pressure. The rotational temperature T _rot of N₂ ⁺ is determined from relative intensity of the R‐branch lines of the N₂ ⁺(B ²Σ_u ⁺–X ²Σ_g ⁺) bands at 427.81 and 419.91 nm and the well‐known Boltzmann plot (BP). Using the same diagnostic technique, the rotationally resolved N₂(C ³Π_u–B ³Π_g) band at 380.49 nm is used to measure T _rot. Under our experimental conditions, T _g is equal to T _rot = 550–650 K for nitrogen molecules and shows a slight increase with the discharge current in the current range 3–10 mA. From the intensity ratio of two consecutive vibrational bands of the same sequence, the N₂(C ³Π_u) and N₂ ⁺(B ²Σ_u ⁺) vibrational temperature T _vib = 3,700–4,000 K is determined. It has been found that N₂ ⁺(B ²Σ_u ⁺) ions have non‐Boltzmann distribution in the helium MHGD, while N₂(C ³Π_u) molecules are populated according to the Boltzmann distribution. Following the Franck–Condon principle, the vibrational distribution of the ground state of N₂(X ¹Σ_g ⁺) molecules has been determined from the N₂(C ³Π_u) distribution using the inversion matrix of elements q _XC(ν ,ν ′).     

Theory of Isotope Effects on He+ Trapping in Solid Hydrogen

We are currently investigating the influence of vibrational effects on the strength of trapping of He⁺ in solid hydrogen. Such effects can lead to an isotope dependence of the trapping energy associated with the hydrogen molecules and He⁺ ion. At the present time, our focus is on the isotope effect for ³He⁺ and ⁴He⁺, which we are studying through the vibrational motions of the trapped He⁺ ions in the potential they experience as they move about their equilibrium positions. The potential governing the vibrations has been obtained from Hartree–Fock cluster calculations of the total energy of the cluster composed of the He⁺ ion and up to the third nearest neighbor hydrogen molecules as a function of the displacement of the He⁺ ion from its trapped position. The energy eigenvalues for the ground vibrational states of ³He⁺ and ⁴He⁺ in this potential come out as 1.29 and 0.96 meV, respectively, leading to corresponding reductions by these amounts in the binding energy of 8.6 eV for both ions without vibrational effects. The difference of these reductions can be considered as an isotope shift, its value for this case being 0.33 meV. From the analysis for these results, it is suggested that isotope shift effects for deuteron and triton in solid D–T would have the same order of magnitude. A procedure for more accurate investigations of the isotope shifts is discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Refined interpretation of broadband radiation from a gas-discharge plasma of a krypton-xenon mixture

The earlier interpretation of the broadband continuum observed in the VUV emission spectra of a gas-discharge plasma in a Kr + Xe mixture is refined. On the assumption that this continuum is caused by the bound-free transitions v,0⁺(³ P ₁) → ε, 0⁺(¹ S ₀) in KrXe* and Xe₂ molecules, the distribution of the population over the vibrational levels v of the states 0⁺(³ P ₁) of both molecules is obtained and the vibrational temperature for different methods of excitation of the spectrum is determined. Internuclear potentials 0⁺(³ P ₁) and 0⁺(¹ S ₀) available from the literature are used. To improve the agreement between the calculated and experimental spectra, it is proposed to modify the positive branch of the potential curve 0⁺(¹ S ₀) of the KrXe* molecule.     

Ab initio nonadiabatic vibrational energies of the hydrogen molecule ion

Nonadiabatic corrections to the four lowest vibrational energy levels of H₂⁺ and HD⁺ are computed by a variational-perturbational method. The results increase the disagreement with experiment of the theoretical 2-1 and 3-2 vibrational transitions and improve the theoretical energy of the 1-0 transition.     

碰撞能及反应物振动激发对Ar+H_2~+→ArH~++H反应立体动力学性质的影响

基于我们最近所构建的Ar+H+2→ArH++H(12A′)反应的新势能面,采用准经典轨线法研究了碰撞能分别为0.48,0.77,1.24 eV以及能量为0.48 eV时反应物不同振动态下Ar+H+2→ArH++H反应的立体动力学性质.结果显示在给定的碰撞能情况下,以及当反应物振动量子数由0变到2时计算的积分反应截面与实验值符合得较好.通过比较发现,碰撞能对此反应k-j′关联函数P(θr)分布的影响大于其受振动激发的影响,并且关于k-k′-j′三矢量相关的函数P(?r)分布以及极化微分反应截面对碰撞能较敏感,同时发现振动激发对P(?r)分布和极化微分反应截面也有较大的影响.     

Vibrational fluorescence of CN− centers in KCl by electronic excitation of neighbouring Tl+ centers

Abstract

Infrared emission from higher vibrational states of CN^? in KCl has been achieved by optically exciting nearby Tl⁺ ions with an excimer laser. The electronic vibrational energy transfer, already known from F_H(CN^?) in alkali halides, leads to population of vibrational states up to at least the tenth level.     

Vibrational properties of the F A (Li+) center in alkali halides

Abstract

The on- or off-axis behavior and the vibrational properties of the F _A (Li⁺) center are investigated in several alkali halides by means of polarized resonant Raman scattering. The observed Raman modes are interpreted and classified according to their nature and frequency. A comparison between on- and off-axis systems and between the vibrational modes of the isolated Li⁺ and the F _A (Li⁺) center reveals a displacement of the Li⁺ equilibrium position parallel to the F _A (Li⁺) defect axis and, due to the small impurity size, away from the adjacent F center.     

Electron stimulated desorption from CO chemisorbed on Pt(111): A dynamical study of positive ion and metastable CO emission

The desorption by electron impact of significant quantities of electronically excited neutral species, CO¹, from CO adsorbed on Pt(111) has been discovered. Comparison of the yield of this species as a function of electron energy, coverage, and temperature, with the yield of O⁺ and C0⁺ has led to the conclusion that the CO¹ species is mainly produced by direct excitation. Studies of the angular distribution of the three ESD-derived species have been made as a function of temperature, and high amplitude bending vibrational modes are observed. Isotope effects in the three desorption channels have been measured.     

Stoßdissoziation von H 2 + - und D 2 + -Ionen

The angular and energy distribution of protons produced by collision-induced dissociations of H ₂ ⁺ ions with energies of 10 and 20 keV were measured in a parabola spectrograph. From these measurements the velocity distribution of the protons in the center of mass system of the H ₂ ⁺ ion can be calculated. This gives information about the type, the abundance, and the anisotropy of the processes involved. The most frequent transitions leading to dissociations are the excitation of the 2pσ_u state, the ionisation of the H ₂ ⁺ ion, the transition into the vibrational continuum, and the electron capture into the 1³ σ _u ⁺ state of the hydrogen. It is shown that the cross section for an electronic transition depends on the velocity of the ion, the distance of the nuclei in the ion, the angle between the internuclear axis and the direction of the primary ion beam, and the excitation energy of the target. The fraction of protons produced by vibrational excitation increases with increasing atomic number of the target. Concerning electronic transitions D ₂ ⁺ ions equal H ₂ ⁺ ions of the same velocity.     

Formation of ultracold RbCs molecules by photoassociation

The formation of ultracold metastable RbCs molecules is observed in a double species magneto-optical trap through photoassociation below the ⁸⁵Rb(5S_1/2) + ¹³³Cs(6P_3/2) dissociation limit followed by spontaneous emission. The molecules are detected by resonance enhanced two-photon ionization. Using accurate quantum chemistry calculations of the potential energy curves and transition dipole moment, we interpret the observed photoassociation process as occurring at short internuclear distance, in contrast with most previous cold atom photoassociation studies. The vibrational levels excited by photoassociation belong to the 5th 0⁺ or the 4th 0^? electronic states correlated to the Rb(5P_{1/2, 3/2}) + Cs(6S_1/2) dissociation limit. The computed vibrational distribution of the produced molecules shows that they are stabilized in deeply bound vibrational states of the lowest triplet state. We also predict that a noticeable fraction of molecules is produced in the lowest level of the electronic ground state.     

The electronic spectrum of silicon monotelluride radical

In the electronic spectrum of silicon monotelluride which has been produced in microwave discharges through sealed tubes, a large number of new bands belonging to theA ¹Π-X ¹Σ⁺ system (3100–3900 Å) and theE ¹Σ⁺-X ¹Σ⁺ system (2800–3100 Å) of Si¹³⁰Te has been observed. The vibrational structure analyses of these band systems have resulted in the determination of improved vibrational constants in all the three electronic states involved in these transitions. An error in the previous determination of the vibrational constants of theE ¹Σ⁺ state has been corrected. An upper limit for the dissociation energy of the silicon monotelluride has been determined to be 40,000 cm^?1.     

Etude de l'energie des electrons ejectes au cours de l'ionisation penning de l'hydrogene moleculaire par les etats metastables 21S et 23S de l'helium

The authors report experiments on the Penning ionization of molecular hydrogen by metastable helium (2¹S and 2³S states). The vibrational structure of the H₂⁺ ion in the state X²Σ_g⁺ is resolved. The relative population of the three first vibrational levels is obtained. The authors also show that a continuum is superposed on the Penning ionization due to the autoionization process.     

Study ofpf-shell nuclei with a symmetry conserving generator coordinate method

Bands based on the 0⁺ ground state and the first excited 0⁺ pairing vibrational state of⁴⁸Ti,⁵²Cr and⁵⁶Fe are studied with the generator coordinate method. The generating wave functions for each value of the angular momentumJ are angular momentum and particle number projected selfconsistent Hartree-Fock-Bogoliubov states where the constrained amount of pairing correlations serves as the generator coordinate. The interaction is given by reaction matrix elements derived from the Hamada-Johnston force. The basis includes the four lowest oscillator shells. The excitation energies of the pairing vibrational states can be reproduced fairly well by the present choice of the generating wave functions, whereas the ground band is not much improved compared to projected Hartree-Bogoliubov calculations. We find that the strength of the pairing correlations in the 0⁺ and 2⁺ states of the ground state and the pairing vibrational bands can be related to data of two-particle transfer reactions. The angular momentum dependence of the pairing correlations and of the moments of inertia are studied. The results show that for a strongly paired ground state the ground state band and the pairing vibrational band intersect. This may produce in the yrast band the anomaly of the moment of inertia known from rare earth nuclei.