Superexcited states of CH4

The energy spectrum of a superexcited state (the different between the total photoabsorption and photoionization cross section) is calculated using ultraviolet photoelectron data for CH₄ and oscillator strength data for the iso-electronic atom, Ne. From this estimate we have concluded that the superexcited state of CH₄ is interpreted in terms of Jahn-Teller distortion of high Rydberg states referring to the ²T₂ state of CH⁺₄. The inconsistency between the data of the UV optical spectrum and results of other measurements or analyses is pointed out and discussed.     

Two-color excitation of NO in a supersonic free jet. Autoionization of high rydberg states

High Rydberg states of NO above the ionization limit have been measured for the isolated molecule in a supersonic free jet by two-color multiphoton ionization. Three Rydberg series (ns, np and nf) were identified, which appeared by rotational and the vibrational autoionization. The rotational structures of the 13s(υ = 1), 13p(υ = 1) and 12f(υ = 1) states have been analyzed in detail. The fluorescence dip spectra for the intermediate A²Σ⁺(3sσ) state have been measured simultaneously and the cross sections of the one-photon absorption to the high Rydberg states from the A²Σ⁺(υ = 1) state have been determined.     

Photoionization of the Kr2 Dimer

The relative photoionization cross section of Kr₂ was determined from 900 to 970 A at a resolution of 0.15 A. Complex molecular autoionization structure is observed throughout the spectrum and has been analyzed in part in terms of Rydberg states converging to the A²Σ⁺_{$\text{1}\text{2}$u} and B²_{Π$\text{3}\text{2g}$} states of the ion.     

Electronic autoionization in carbon monoxide: the effects of the vibrational motion

New continuous measurements of the vibrationally resolved photoionization cross sections of CO⁺ X ²Σ⁺ and A ²Π between 63 and 83 nm are reported. We assign the Rydberg series converging to CO⁺ A ²Π. The effects of the vibrational motion are interpreted on the basis of the Condon approximation. This approximation is shown to allow a qualitative understanding of the decay of the Rydberg series converging to the A ²Π and B ²Σ⁺ states of CO⁺.     

Photoionization of Xe2, Xe3 and Xe4 in the 1024–1113 Å region

The mass spectra of Xe _n ⁺ clusters (n=2–13) were recorded using a supersonic beam and an ion time-of-flight mass analyser. The yield of Xe ₂ ⁺ , Xe ₃ ⁺ and Xe ₄ ⁺ cluster ions was measured with a resolution of 0.1 Å (1 meV) in the 1024–1113 Å (11.1–12.1 eV) region. Autoionizing Rydberg series of Xe₂ converging to theC ²_3/2u state of Xe ₂ ⁺ were observed in the spectrum of Xe ₂ ⁺ . The photoionization yield of Xe ₃ ⁺ and Xe ₄ ⁺ ions each displayed similar broad features that contained no fine structure corresponding to vibrational states. The broad features were assigned to autoionizing Rydberg series by analogy with the dimer ion spectrum.     

Semidiffuse states of diatomic molecules: Configuration interaction studies of the lowest 2Σ+ and 2Δ states of NS,SiF, and CCl

It has been shown by ab initio configuration-interaction methods that the lowest ²Σ⁺ states of NS and SiF are ‘semidiffuse’ states, like the B ²Σ⁺ state of PO. The lowest ²Σ⁺ state of CCl also appears to be semidiffuse, although here the situation is not so clear. Semidiffuse states require diffuse orbitals in the wavefunction, but they are not Rydberg states. The second ²Σ⁺ state of each molecule is shown to be the lowest ns Rydberg state, whereas the third ²Σ⁺ state is a valence state for NS and CCl, and a 4po Rydberg state for SiF. The lowest ²δ state of each molecule derives from the 7σ → 3π valence configuration. Comparison with available experimental information shows, in general, good agreement.     

High-resolution laser spectroscopy of H2 in a fast beam

High-resolution laser photofragment spectroscopy is performed in a fast beam of H₂c³Π_u⁻ formed by near resonant charge exchange. The observed linewidths allow partial resolution of the fine and hyperfine structure in the 1s3d g ³Σ⁺_g Rydberg state. Simulations of the spectra indicate that the hyperfine splittings are very close to those of H⁺₂ as expected for Rydberg states.     

Rydberg states of the K2 molecule studied by laser spectroscopy in a supersonic beam

Rydberg states of potassium dimer have been studied in a crossed laser-molecular beam experiment. The K₂ molecules were formed in a supersonic expansion and excited by low-power cw dye laser. Two different excitation schemes have been used: The first scheme uses a single mode ring dye laser to induce near resonant two-photon transitions while in the second scheme stepwise excitation with two dye lasers is used. In each case excitation of Rydberg levels was detected by monitoring the ionization signal resulting from three-photon absorption. We report a detailed study of 700 two-photon resonances between 625 nm and 650 nm. Most of these signals can be assigned to transitions from the X¹σ _g ⁺ to¹σ _g ⁺ ,¹Π _g , and^1Δ _g states, which are all enhanced by the B¹Π _u intermediate state. Accurate rotational constants are given for the populated vibrational levels of these states. By stepwise excitation of Rydberg levels via theB ¹Π _u state we identify 3 series of Rydberg states as¹Δ _g (4S+nD),¹Σ _g ⁺ (4S+nD), and¹Σ _g ⁺ (4S+nS) with principal quantum numbers 7≦n≦20. Molecular constants of these and other observed but as yet unidentified states are given; quantum defects and dissociation energies are discussed.     

Potential energy curves and spectral properties for electronic states of F2 and F+2

Potential energy (PE) curves for the Rydberg states of F₂, and for the ground and lowest two electronic states each of symmetry ²Π_g,u, ²Δ_g,u and ²Σ^±_g,u of F⁺₂, have been obtained using modest-sized configuration-interaction calculations. These PE curves have been used to calculate spectroscopic constants for the electronic states and the results agree reasonably well with the limited experimental and theoretical results previously reported. The theoretical PE curves for the Rydberg states of F₂ are found to be strongly perturbed by valence-Rydberg-ionic interactions and these perturbations appear to be responsible for certain features in recently reported electron energy-loss spectra in F₂. The corresponding electronic wavefunctions have been used to calculate the electronic transition moment, as a function of the internuclear distance, for dipole-allowed transitions between the lowest excited electron state of each symmetry and the appropriate ground electronic state. The radiative emission probabilities, natural lifetimes, and absorption oscillator strengths, for each band system, are also reported here. The predicted lifetimes for vibrational levels of the A ²Π_u of electronic state in F⁺₂ vary from 1.3–1.5 μs and agree reasonably well with the single available set of measurements. The predicted radiative lifetimes for the higher electronic states of F⁺₂ are substantially longer and fall into the range 5–100 ms.     

Electronically excited and ionized states of the chlorine molecule

Potentials curves for the ground and excited states of the chlorine molecules and its positive and negative ions have been calculated by means of the MRD-CI method. The standard AO basis employed consists of 74 functions including two atomic d and one set of s and p bond species, and the results at the corresponding full CI level are estimated for each state via a perturbation correction. Special emphasis is placed upon the treatment of Rydberg-valence mixing in this system, which phenomenon is found to be essential to the understanding of Cl₂ electronic absorption spectrum. All singlet states which correlate with the lowest dissociation limit plus many others which go to ionic Cl⁺+Cl^? or Rydberg Cl+Cl asymptotes are given explicit consideration. Among the triplet species of Cl₂ which dissociate into the ground state atoms only the ³Π_u state is not repulsive. The calculated D₀ value for the ground state is 2.455 eV compared to the experimental value of 2.475 eV, while the vertical ionization energy and electron affinity are found to be 11.48 and 2.38 eV respectively, also in very good agreement with the corresponding measured data of 11.50 and 2.51 ± 0.1 eV. In addition to Cl₂ laser line is confirmed to result from a ³Π_g → ³Π_u emission, whereby the calculated downward vertical transition energy of 4.86 eV fits in quite well with the known location of this line at 4.805 eV. The first two dipole-allowed transitions from the ground state of chlorine involve ¹Σ_u⁺ and ¹Π_u states which are calculated to be nearly isoenergetic, and these results also match very well with the location of the first absorption band in this spectrum. Finally quite similarly as in O₂ it is found that an avoided crossing between Rydberg and valences states produces a relatively steep potential well for an upper state (2 ¹Σ_u⁺), whose location concides with that of a second absorption band recently observed in synchrotron radiation studies.     

Configuration-Interaction study of lower excited states of O2: Valence and rydberg characters of the two lowest 3Σu − states

Configuration-interaction calculations, with an extended basis, are carried out on the ground and lower excited states of O₂ and O₂⁺ at and near the equilibrium internuclear distance (R = 2.3 a.u.) of the ground state of O₂. Particular attention has been paid to the two lowest ³Σ_u^? states, and the mixing of the valence and Rydberg characters in these states are studied. The lowest ³Σ_u^? state is a Rydberg-type state for R < 2.3 a.u., but becomes valence-type for R ? 2.3 a.u. The second ³Σ_u^? state, which is 1.6 eV above the lowest ³Σ_u^? at R = 2.3 a.u., changes its character from Rydberg to valence, valence to Rydberg, and then to valence again when R increases from 1.9 to 3.1 a.u. Satisfactory agreement between the calculated and experimental vertical excitation energies is obtained.     

Translational energy distribution of the excited hydrogen atom produced by controlled electron impact on HCl

The translational energy distribution of an atom can be calculated by differentiating the Doppler line shape of its emission line taken at a high optical resolution. The Balmer-β line of the excited hydrogen atom (n = 4) produced by electron impact on HCl has been measured at a high resolution (0.033Å) and at two angles (55° and 90°) with respect to the electron beam. The translation energy distribution depends on the electron energies and has almost two groups of components: ≈ 5 eV (fast) and ≈ eV (slow). Anisotropy is imporant for the slow component. The excitation function shows the corresponding structures. It is concluded that Rydberg states converging to the ²Π state of HCl⁺ produce the fast component and Rydberg states converging to the repulsive HCl⁺ states which cross the ²Σ⁺ state produce the slow component.     

Dissociative recombination of HeH+. I. Rovibrational spectrum of HeH Rydberg states

The repulsive ground electronic state X²Σ⁺ of HeH is strongly coupled to the Rydberg states at small interatomic distances. Such large couplings also occur between some of the Rydberg states. HeH⁺ ions that capture an electron in a Rydberg state end up in separated He and H atoms by indirect predissociation. This paper presents a study of potential functions and pertinent matrix elements involving the lowest electronic states: the ²Σ⁺ states, X, A, C, and D, and the ²Π states B and E. Individual transition rates as well as total radiative and non-radiative lifetimes have been computed for the lowest vibrational and rotational levels. Received: 22 June 1998 / Accepted: 21 August 1998 / Published online: 12 October 1998     

Translational energy distributions and production mechanisms of the excited hydrogen atom (n = 3,4) produced in e-NH3 collisions

The Balmer α and β lines produced in e-NH₃ collisions have been measured precisely with the use of a Fabry-Perot interferometer. These lines are not polarized. The translational energy distributions of (H^*(n = 3,4) were determined from analysis of Doppler lineshapes and have five components; their peaks lie at 1, 3, 2, 4–5 and 8–12 eV. The excitation function [H^*(n = 4)] has five thresholds at 22.5, 29.0, 33.3, 38.9 and 41.7 eV, and indicates that five dissociation processes contribute to the formation of H^*. Excitation to the Rydberg states converging to the (2a₁)^?1 state of NH₃⁺ is a major process for the formation of the first and the second components. Doubly excited Rydberg states play important roles in the dissociative excitation of NH₃.     

MRD CI calculations of excited states of the SiH3 radical,including potential curves for the inversion mode and the dissociation SiH3 → SiH2 + H

Using the MRD CI method and large basis sets the vertical spectrum of silyl radical (SiH₃) has been calculated. The lowest excited state is the 4s Rydberg state, 41000 cm⁻¹ (5.2 eV) above the ground state. Only one excited valence state (2²E) was encountered, all other states are of Rydberg type. From potential curves for the inversion mode (symmetric bending motion) it was inferred that all Rydberg states are planar, whereas the valence excited state is highly pyramidalized. The investigation of the dissociation reaction SiH₃ → SiH₂ + H leads to the conclusion that the first excited state is dissociative.     

Polarization labelling spectroscopy of molecular Li2 rydberg states

A series ofnd δ ¹ Δ _g Rydberg states of the Li₂ molecule has been measured using the polarization labelling technique. The experimental term values and the quantum defects derived from them, are compared with theoretical values obtained from ab initio calculations. The different physical effects contributing to the quantum defects are discussed. It turns out that perturbations of the Rydberg states by the doubly excited configurations with the atomic asymptotes 2p+2p have a significant influence on the quantum defects.     

Angle- and spin-resolved photoelectron spectroscopy of thepπ outer valence shell of HBr molecules

Using circularly polarized synchrotron radiation, the photoionization of HBr molecules was studied by angle- and spin-resolved photoelectron spectroscopy in the photon energy range from 11.7 eV to 21 eV. For photoelectrons corresponding to the final ionic states HBr⁺ X ²Π_3/2(v=0) andX ²Π_1/2(v=0), the energy dependence of the dynamical photoionization parameters was measured and compared with ab initio calculations for HBr⁺ by Raseev et al. and RRPA calculations for Kr⁺ by Huang et al., This comparison indicates that, for energies above the electronic autoionization region, photoemission from the outer valence orbital exhibits distinct atomic behavior. By combining the experimental data for the cross section σ and the spin polarization parameter A, sums of partial cross section contributions to σ were determined and analyzed to obtain specific information on the outgoing partial electron waves. Furthermore, the validity of the so-called non-relativistic relationships for the dynamical photoionization parameters was tested as a function of equal photon and kinetic photoelectron energy, respectively.     

Oscillator strength measurements of the 5s5p 3P1 → 5snd 3D2 Rydberg transitions of cadmium

We report oscillator strengths distribution in the bound region of cadmium corresponding to the 5s5p ³P₁ → 5snd ³D₂ (21 ≤ n ≤ 52) Rydberg transitions. The experiment was performed using two frequency doubled dye lasers simultaneously pumped by a common Nd:YAG laser in conjunction with an atomic beam set-up. The absolute photoionization cross section of the 5s5p ³P₁ intermediate state at the 5s ²S_1/2 ionization threshold has been measured as 20 (4) Mb using the saturation technique. The measured value of the photoionization cross section at threshold is used to extract the f-values of the above mentioned Rydberg transitions.     

On Metal-Atom Clusters IV. Photoionization thresholds and multiphoton ionization spectra of alkali-metal molecules

The investigation of electronic and structural parameters of metal molecules as a function of size may be decisive for understanding and control of heterogeneous catalysis with finely divided metals. Metal-atom clusters can be prepared by several methods, most of which yield a molecular mixture only. Expansion of an atomic vapour into vacuum through a supersonic nozzle creates a complex cluster-spectrum which has been investigated by photoionization using a mass-spectrometer as selective detector. Broad band single photoionization ( PI. ) yields the abundances and ionization thresholds for Na_x(x?16), K_x(x?12) and Na_xK_y(x+y?6). Rough indications about other deactivation channels of excited alkali-molecules are obtained from an analysis of the photoionization efficiency (PIE.) curves. Two-photon PIE. curves with narrow-band (laser) light sources give an accurate photoionization threshold value and detailed information on ionization processes. Two-photon ionization spectra via a real intermediate state reached by laser excitation are equivalent to normal absorption spectra, if the exciteation step is controlled by the true transition probabilities. By investigation of the power dependence of the ion current of Na as a function of the wavelength of the tunable cw dye laser (excitation) and of the ionizing Ar⁺- or Kr⁺-laser, conditions under which true spectra are obtained have been clarified, in good agreement with a photon-kinetic model of the processes involved. Vibronic and rovibronic spectra of several transitions in Na₂ and K₂ have been measured. Similarly a spectrum of Na₃ has been determined mass-selectively. The scope of the new method for an absorption spectroscopy in molecular beams is discussed.     

Potential energy curves of several excited states of the Ne2* excimer: Assignment of the transient absorption spectra of the excimer

Most of the excited states of Ne₂, which are correlated with the Rydberg state transitions 2p → 3s, 3p, and 4s of Ne, are studied by ab initio CI calculations. Two transient absorption spectra from the lowest excimer state Σ_u⁺ recently observed by Arai et al., are discussed on the basis of calculated potential energy curves. Possible assignments are presented. The calculated transition energies are in good agreement with the observed ones.