Study of the lowest electronic states of Xe2, XeKr, and XeAr molecules by the method of multiphoton resonance ionization

Khodorkovskii, M. A.; Belyaeva, A. A.; Rakcheeva, L. P.; Serdobintsev, P. Yu.; Pastor, A. A.; Melnikov, Andrei G.; Timofeev, N. A.; Hallin, R.; Seigbahn, K.

doi:10.1134/s0030400x08050068

Cited by 10 publications

(11 citation statements)

References 16 publications

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“…8(b)) would favour excitation of tunneling/predissociation resonances between 77400 and 77500 cm −1 . Such resonances lie in the range where broad spectral features have been observed in previous studies of the absorption spectrum 9, 30 and the (3 + 1) resonance-enhanced multiphoton ionization (REMPI) spectrum 37 of ArXe. In particular, we believe that our potential model provides an attractive explanation for the broad resonance observed at ∼ 77400 cm −1 in the (3 + 1) REMPI study.…”

Section: Perturbation Of the Vibrational Structure And Potential Modementioning

confidence: 66%

“…In particular, we believe that our potential model provides an attractive explanation for the broad resonance observed at ∼ 77400 cm −1 in the (3 + 1) REMPI study. 37…”

Section: Perturbation Of the Vibrational Structure And Potential Modementioning

confidence: 99%

“…single-photon VUV spectra 9,[28][29][30][31][32] and resonance-enhanced multiphoton ionization spectra. 21,22,[33][34][35][36][37][38] Several electronically excited states located in the vicinity of the Ar( 1 S 0 ) + Xe* (Xe* = 6s [ ) dissociation limits have been assigned from direct observation of the rotational structure (see, e.g., Ref. 29), from the dependence of the observed intensity distributions on the polarization of the radiation used to record multiphoton excitation spectra (see, e.g., Ref.…”

Section: Introductionmentioning

confidence: 99%

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Structure and dynamics of the electronically excited C 1 and D 0+ states of ArXe from high-resolution vacuum ultraviolet spectra

Piticco

Schäfer

Merkt

2012

The Journal of Chemical Physics

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Vacuum ultraviolet spectra of the C 1 ← X 0(+) and D 0(+) ← X 0(+) band systems of ArXe have been recorded at high resolution. Analysis of the rotational structure of the spectra of several isotopomers, and in the case of Ar(129)Xe and Ar(131)Xe also of the hyperfine structure, has led to the derivation of a complete set of spectroscopic parameters for the C 1 and D 0(+) states. The rovibrational energy level structure of the C 1 state reveals strong homogeneous perturbations with neighboring Ω = 1 electronic states. The analysis of isotopic shifts led to a reassignment of the vibrational structure of the C 1 state. The observation of electronically excited Xe fragments following excitation to the C state rotational levels of f parity indicates that the C state is predissociated by the electronic state of 0(-) symmetry associated with the Ar((1)S(0)) + Xe(6s(')[1/2](0) (o)) dissociation limit. The observed predissociation dynamics differ both qualitatively and quantitatively from the behavior reported in previous investigations. An adiabatic two-state coupling model has been derived which accounts for the irregularities observed in the rovibronic and hyperfine level structure of the C 1 state. The model predicts the existence of a second state of Ω = 1 symmetry, supporting several tunneling/predissociation resonances located ~200 cm(-1) above the C 1 state.

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Section: Perturbation Of the Vibrational Structure And Potential Modementioning

confidence: 66%

“…In particular, we believe that our potential model provides an attractive explanation for the broad resonance observed at ∼ 77400 cm −1 in the (3 + 1) REMPI study. 37…”

Section: Perturbation Of the Vibrational Structure And Potential Modementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structure and dynamics of the electronically excited C 1 and D 0+ states of ArXe from high-resolution vacuum ultraviolet spectra

Piticco

Schäfer

Merkt

2012

The Journal of Chemical Physics

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“…In the present paper we continue a series of studies of excited states of rare gas (RgRg ) diatomic molecules by multiphoton resonance laser ionization [2][3][4][5]. This method allows us to obtain electronic spectra of unstable van der Waals molecules generated in a supersonic molecular beam in the VUV region.…”

Section: Introductionmentioning

confidence: 97%

Electronic spectra of ArXe molecules in the region of Xe* (6s′, 6p, 5d), 77 000–80 200 cm⁻¹, using resonantly enhanced multiphoton ionization

Khodorkovskii

Murashov

Артамонова

et al. 2010

J. Phys. B: At. Mol. Opt. Phys.

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The excited electronic states of ArXe molecules in the region 77 000–80 200 cm−1 were studied using the (2+1) and (3+1) resonance-enhanced multiphoton ionization methods. The use of different methods of multi-photon excitation and Ar+ ion registration allowed us to obtain some new data. Molecular constants were obtained for previously unknown excited states of molecules with the following dissociation limits: ArXe* → Ar1S0+Xe*6р[5/2]3 with Ω = 2, 3 symmetry; Ar1S0+Xe*6p[3/2]2 with Ω = 1, 2 symmetry; Xe0S1 → Xe*6s′[1/2]01 with Ω = 0+ symmetry.

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“…The electronically excited states of the heteronuclear rare-gas dimers located close to one of the dissociation limits Rg ′ * + Rg( 1 S 0 ) (Rg, Rg ′ = Ne, Ar, Kr, Xe and Rn), and in particular the C and D states of ArXe and KrXe, are ideal systems for such an investigation. This scientific goal has been pursued in several previous investigations of the low-lying electronic states of KrXe, most notably in studies by VUV absorption and emission spectroscopy [1,2,3,4], resonant multiphoton ionization spectroscopy [5,6,7,8,9,10,11,12,13,14,15] and photoelectron spectroscopy [16,17]. In these studies, the vibrational structure of the electronic spectra could be resolved, insight could be gained into the main properties of the electronically excited states, and the dominant spectral perturbations could be identified.…”

Section: Introductionmentioning

confidence: 99%

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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Study of the lowest electronic states of Xe2, XeKr, and XeAr molecules by the method of multiphoton resonance ionization

Cited by 10 publications

References 16 publications

Structure and dynamics of the electronically excited C 1 and D 0+ states of ArXe from high-resolution vacuum ultraviolet spectra

Structure and dynamics of the electronically excited C 1 and D 0+ states of ArXe from high-resolution vacuum ultraviolet spectra

Electronic spectra of ArXe molecules in the region of Xe* (6s′, 6p, 5d), 77 000–80 200 cm⁻¹, using resonantly enhanced multiphoton ionization

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+

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Study of the lowest electronic states of Xe2, XeKr, and XeAr molecules by the method of multiphoton resonance ionization

Cited by 10 publications

References 16 publications

Structure and dynamics of the electronically excited C 1 and D 0+ states of ArXe from high-resolution vacuum ultraviolet spectra

Structure and dynamics of the electronically excited C 1 and D 0+ states of ArXe from high-resolution vacuum ultraviolet spectra

Electronic spectra of ArXe molecules in the region of Xe* (6s′, 6p, 5d), 77 000–80 200 cm−1, using resonantly enhanced multiphoton ionization

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+

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Product

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Electronic spectra of ArXe molecules in the region of Xe* (6s′, 6p, 5d), 77 000–80 200 cm⁻¹, using resonantly enhanced multiphoton ionization