Mass-resolved VUV laser spectra in the vicinity of the Rydberg minimum of the 1 1∑+u state of Cl2

Wang, P.; Okuda, I.; Dimov, S. S.; Lipson, R. H.

doi:10.1016/0009-2614(94)01092-7

Cited by 6 publications

(4 citation statements)

References 15 publications

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“…From the electronic configurations of ion-pair states 1 3 Σ u − and 2 3 Π u , it is seen that direct excitations to them involve two-electron excitation processes, and hence have low transition probabilities. The direct excitation to 1 1 Σ u + has a large transition dipole moment, which has already been observed in spectroscopic studies using photon energies ∼8 eV. − ,, However, for photon energies ∼12.5 eV, the vertical excitation to 1 1 Σ u + is out of the Franck−Condon region that is indicated in Figure by the wave packet of the vibrational ground-state Cl 2 (X 1 Σ g + ), therefore, the direct ion-pair dissociation via 1 1 Σ u + is difficult.…”

Section: Resultsmentioning

confidence: 84%

“…The direct excitation to 1 1 Σ u + has a large transition dipole moment, which has already been observed in spectroscopic studies using photon energies ∼8 eV. [19][20][21]29,30 However, for photon energies ∼12.5 eV, the vertical excitation to 1 1 Σ u + is out of the Franck-Condon region that is indicated in Figure 9 by the wave packet of the vibrational ground-state Cl 2 (X 1 Σ g + ), therefore, the direct ion-pair dissociation via 1 1 Σ u + is difficult. ) can be found in Table 2 using the index numbers.…”

Section: T H I S C O N T E N T Imentioning

confidence: 96%

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Ion-Pair Dissociation Dynamics of Cl₂: Adiabatic State Correlation

Zhou

Hao

2008

J. Phys. Chem. A

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The ion-pair dissociation dynamics of Cl2 -->(XUV) Cl(-)((1)S0) + Cl(+)((3P(2,1,0)) in the range 12.41-12.74 eV have been studied employing coherent extreme ultraviolet (XUV) radiation and the velocity map imaging) method. The ion-pair yield spectrum has been measured, and 72 velocity map images of Cl(-)((1)S0) have been recorded for the peaks in the spectrum. From the images, the branching ratios among the three spin-orbit components Cl(+)((3)P2), Cl(+)((3)P1) and Cl(+)((3)P0) and their corresponding anisotropic parameters beta have been determined. The ion-pair dissociation mechanism is explained by predissociation of Rydberg states converging to ion-core Cl2(+)(A(2)Pi(u)). The Cl(-)((1)S0) ion-pair yield spectrum has been assigned based on the symmetric properties of Rydberg states determined in the imaging experiments. The parallel and perpendicular transitions correspond to the excitation to two major Rydberg series, [A(2)Pi(u)]3d pi(g), (1)Sigma(u)(+) and [A(2)Pi(u)]5s sigma(g), (1)Pi(u), respectively. For the production of Cl(+)((3)P0), it is found that all of them are from parallel transitions. But for Cl(+)((3)P1), most of them are from perpendicular transitions. The production of Cl(+)((3)P2) is the major channel in this energy region, and they come from both parallel and perpendicular transitions. It is found that for most of the predissociations the projection of the total electronic angular momentum on the molecular axis (Omega) is conserved. The ion-pair dissociation may be regarded as a probe for the symmetric properties of Rydberg states.

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Section: Resultsmentioning

confidence: 84%

Section: T H I S C O N T E N T Imentioning

confidence: 96%

Ion-Pair Dissociation Dynamics of Cl₂: Adiabatic State Correlation

Zhou

Hao

2008

J. Phys. Chem. A

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“…The dominant interaction between the diabatic 4pπ Rydberg state and the third tier ion-pair state that dissociates to Cl + ( 1 D g ) + Cl - ( 1 S g ) yields a lower energy adiabatic level (called 1 1 ), which has a double-well potential energy curve. This structure has now been satisfactorily characterized by several single-photon synchrotron − and VUV laser studies. − …”

Section: Introductionmentioning

confidence: 90%

“…This structure has now been satisfactorily characterized by several single-photon synchrotron [2][3][4] and VUV laser studies. [5][6][7] For many years, however, the spectroscopy of the higher energy adiabatic 2 1 Σ u + state resulting from the avoided crossing described above was much more poorly understood even though Douglas first reported rough VUV absorption wave numbers for the 2-X transition as early as 1981. 8 Recently, this situation has been reversed through a judicious combination of theory 1 and VUV laser experimentation.…”

Section: Introductionmentioning

confidence: 99%

Rotational Analyses for Selected Bands of the 2 ← X¹ Transition of Cl₂

1997

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Rotational analyses are presented for selected bands of the 21 (v‘= 1−3) ← X1 (v‘‘ = 0) transition of supersonically cooled Cl2, recorded in fluorescence excitation near λ ≤ 128 nm with a tunable, coherent, and monochromatic vacuum ultraviolet laser generated by four-wave difference mixing in Kr gas. Absolute J-numbering was established in part by spectral simulation. Although the band system is perturbed, the effective rotational constants derived in this work are consistent with theoretical calculations that place the excited two-state equilibrium bond length at ∼2.1 Å.

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