Interactions of rare gas cations with lighter rare gas atoms

Viehland, Larry A.; Gray, Benjamin R.; Wright, Timothy G.

doi:10.1080/00268971003604583

Cited by 17 publications

(7 citation statements)

References 44 publications

(33 reference statements)

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“…[9], they also confirm the values of the dissociation energies of the X 1/2 and A 1 3/2 states determined in Ref. [9] which differ from the values determined ab initio, as already noted by Viehland et al [45]. In each panel, the experimental spectra are shown as lower, inverted traces, and the calculated spectra as upper traces.…”

Section: The a 1 3/2 ← C 0 + Photoionizing Transition Of Krxesupporting

confidence: 87%

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High-resolution spectroscopic study of the C 0+ and D 1 Rydberg states of KrXe and of the X 1/2 and A1 3/2 states of KrXe+

Piticco

Merkt

2013

Journal of Molecular Spectroscopy

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The electronic spectrum of the C 0 + , D 1 ← X 0 + transitions of KrXe has been studied at high resolution in the vicinity of the Kr(1 S 0) + Xe 6p[5/2] 2 dissociation limit by resonance-enhanced (1+1 ′) two-photon ionization spectroscopy. The rotational structure of 13 bands, 5 and 8 of which correspond to transitions to levels of 0 + and 1 symmetry, respectively, were observed in the spectra of several isotopomers, and the hyperfine structure in the spectrum of the Ω = 1 levels of 84 Kr 129 Xe was determined. The five transitions to levels of 0 + symmetry form a regular progression of bands characterized by a regular rotational structure and corresponding to high vibrational levels (with v = 16 − 20) of the C 0 + state. The C 0 + state is found to possess significant X 1/2, A 1 3/2 and A 2 1/2 ion-core character in combination with an excited electron of 6pσ, 6pπ and 6sσ character, respectively, and to correlate adiabatically to the Kr(1 S 0) + Xe 6s[1/2] o 1 dissociation limit. The transition to the eight levels of Ω = 1 symmetry form a very irregular progression both as far as spectral positions and intensities are concerned. Rotational levels of f-symmetry, accessed via Q-branch transitions, are weakly predissociated by a repulsive level associated with the Kr(1 S 0) + Xe 6s[1/2] o 0 limit. A local perturbation in the rotational structure of the fourth level of Ω = 1 symmetry enabled the identification of a so far unobserved predissociative level of Ω = 1 or Ω = 2 symmetry with band center near 77318.5 cm −1. The determination of the band centers, rotational constants and isotopic shifts of the Ω = 1 levels led to the conclusion that the level structure is affected by homogeneous perturbations and that at least two electronic states of Ω = 1 symmetry contribute to the spectrum of KrXe in this spectral region. Modelling the observed rovibronic structure using a coupling model involving low vibrational levels of a weakly bound Ω = 1 state associated with the Kr(1 S 0) + Xe 6s[1/2] o 1 dissociation limit and high vibrational levels of a more strongly bound state associated with the Kr(1 S 0) + Xe 6p[5/2] 2 dissociation limit enabled us to reproduce the observed values of the rotational constants, vibronic positions and intensity distribution in a qualitatively satisfactory manner. However, the model failed to account for the observed isotopic shifts. Rotationally resolved photoelectron spectra of the KrXe + X 1/2 ← KrXe C 0 + and KrXe + A 1 3/2 ← KrXe C 0 + ionizing transitions were recorded from selected rotational levels of selected isotopomers of KrXe. The rotational levels of the X 1/2 state of KrXe + group as pairs of levels of opposite parity and have a spin-rotation coupling constant γ of approximately −2B, as a consequence of pure precession. The rotational level structure of the low-lying electronic states of KrXe + thus appear to form the same patterns as the corresponding states of ArXe + .

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Section: The a 1 3/2 ← C 0 + Photoionizing Transition Of Krxesupporting

confidence: 87%

“…The equilibrium internuclear distance [R e = 3.71(66) Å] estimated from the rotational constants of the A 1 3/2 state and their v dependence lie halfway between the value obtained ab initio by Viehland et al [45] and that of the semi-empirical potential functions determined in Ref. [9].…”

Section: The a 1 3/2 ← C 0 + Photoionizing Transition Of Krxesupporting

confidence: 56%

High-resolution spectroscopic study of the C 0+ and D 1 Rydberg states of KrXe and of the X 1/2 and A1 3/2 states of KrXe+

Piticco

Merkt

2013

Journal of Molecular Spectroscopy

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“…In a recent publication, Viehland et al 21 noted the discrepancy between the dissociation energies they calculated ab initio with the values determined from experimental data…”

Section: A Molecular Constants and Potential-energy Curves Of The X mentioning

confidence: 99%

“…7 The potential model indicates that the electronic states associated with the Xe + + Ar and Xe + Ar + dissociation limits are mixed at short range and that it is necessary to consider charge-exchange interactions to accurately describe the measured vibronic energies of ArXe + . Recently, Viehland et al 21 have calculated the potential-energy functions of several heteronuclear rare-gas dimer cations ab initio and compared them with the potentialenergy functions derived from experimental data. Although the overall agreement was reported to be satisfactory in the case of ArXe + , Viehland et al also pointed at several discrepancies, primarily concerning the dissociation energies, and to a lesser extent also the equilibrium internuclear distances, and questioned the reliability of the experimental data.…”

Section: Introductionmentioning

confidence: 99%

Rotationally resolved PFI-ZEKE photoelectron spectroscopic study of the low-lying electronic states of ArXe+

Piticco

Merkt

2012

The Journal of Chemical Physics

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Rotationally resolved pulsed-field-ionization zero-kinetic-energy photoelectron spectra of the X 1/2, A(1) 3/2, and A(2) 1/2 electronic states of the ArXe(+) molecular ion have been recorded following resonant (1+1') two-photon excitation via selected rovibrational levels of the C 1 and D 0(+) states of selected isotopomers of the ArXe molecule. Using rovibronic selection and propensity rules for the photoionization out of these intermediate molecular states enabled the determination of the parity of the molecular-ion levels and of the magnitude and sign of the Ω-doubling constants of the coupled X 1/2 (p ≈ 4B) and A(2) 1/2 (p ≈ -2B) states of ArXe(+). The results indicate that these molecular-ion states can be approximately described using Mulliken's second variant of Hund's angular momentum coupling case (c), for which J(a), the total electronic and spin angular momentum of the two atoms, is a good quantum number (semi-united atom). The analysis of the rotational structure enabled the derivation of improved values of the dissociation energies, equilibrium distances, and molecular constants for the X 1/2, A(1) 3/2, and A(2) 1/2 states of ArXe(+).

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“…Типичный вид кривых потенциальной энергии исследуемых ионов приведен на рис. 2 по данным работ [62][63][64]. При рассмотрении процессов ДВ гетероядерных…”

Section: результаты и обсуждениеunclassified

Прямое Диссоциативное Возбуждение Гетероядерных И Гомоядерных Ионов Инертных Газов Электронным Ударом

Кислов¹,

Нариц²,

Лебедев³

2020

Журнал Технической Физики

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A theoretical description of the process of dissociative excitation of a molecular ion by electron impact in the case of effective population of a huge number of its vibrational-rotational levels is presented. Our consideration is based on the quantal version of the theory of non-adiabatic transitions between the electronic terms of a molecular ion combined with replacing the summation over vJ-levels by integration over v and J. Semianalytical formulas are derived for the integral contribution of the entire vibrational-rotational quasicontinuum to the cross sections, $\sigma_T^{\mathrm{de}}(\varepsilon)$, and the rate constants, $\alpha^{\mathrm{de}}(T, T_e)$ of the process under study in a plasma with temperatures $T_e$ and $T$ of its electronic and ionic components. The developed theory is used to study the processes of dissociative excitation of heteronuclear (HeXe$^{+}$ and ArXe$^{+}$) and homonuclear (Ar$_2^{+}$ and Xe$_2^{+}$) ions of inert gases. We demonstrate a strong dependence of the results on the ion dissociation energy and large differences in the behavior and characteristic values of $\sigma_T^{\mathrm{de}}(\varepsilon)$ and $\alpha^{\mathrm{de}}(T, T_e)$ for these systems in different ranges of electron energy, $\varepsilon$, and temperatures $T_e$ and $T$. The regions of dominance of the contributions of two competing channels are determined: direct dissociative excitation and dissociative recombination into total cross sections and the rate constants of destruction of rare gas molecular ions by electron impact. Analyzing behavior of the differential rate constants of dissociative excitation per unit range of electron energy in the final channel of reaction we demonstrate qualitative differences in the dynamics of this process for weakly bound and moderately bound molecular ions.

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Interactions of rare gas cations with lighter rare gas atoms

Cited by 17 publications

References 44 publications

High-resolution spectroscopic study of the C 0+ and D 1 Rydberg states of KrXe and of the X 1/2 and A1 3/2 states of KrXe+

High-resolution spectroscopic study of the C 0+ and D 1 Rydberg states of KrXe and of the X 1/2 and A1 3/2 states of KrXe+

Rotationally resolved PFI-ZEKE photoelectron spectroscopic study of the low-lying electronic states of ArXe+

Прямое Диссоциативное Возбуждение Гетероядерных И Гомоядерных Ионов Инертных Газов Электронным Ударом

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