A predissociative triplet Rydberg state of the nitrogen molecule studied by near-infrared diode laser kinetic spectroscopy

Hashimoto, Tatsuya; Kanamori, Hideto

doi:10.1016/j.jms.2005.10.008

Cited by 12 publications

(17 citation statements)

References 16 publications

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“…This observation follows the recent detailed characterization of the G͑v =0͒ state by Hashimoto and Kanamori, 22 who performed a nearinfrared diode-laser kinetic-spectroscopic study of the G 3 ⌸ u -E 3 ⌺ g + ͑0,0͒ transition. Transition energies for JЉ Յ 10, from the line assignments indicated in Fig.…”

supporting

confidence: 76%

“…However, in two recent investigations, both the G͑v =0͒ and F͑v =0͒ states have been studied at high resolution, revealing rotational structure for the first time. First, Hashimoto and Kanamori 22 performed a near-infrared diode-laser spectroscopic study of the Rydberg-Rydberg transition G 3 ⌸ u -E 3 ⌺ g + ͑0,0͒, with a Doppler-limited resolution of ϳ0.01 cm −1 full width at half maximum ͑FWHM͒, enabling rotational analysis and determination of the Ͼ0.1 cm −1 FWHM predissociation linewidth for the G͑v =0͒ state. Second, in measurements related to the work to be presented here, Sprengers et al 23 used two-photon ionization laser spectroscopy, with an effective resolution of ϳ0.06 cm −1 FWHM, to study the extremeultraviolet ͑EUV͒ F 3 ⌸ u -X 1 ⌺ g + ͑0,0͒ forbidden transition, obtaining spectroscopic parameters and revealing a predissociation linewidth of ϳ0.45 cm −1 FWHM for the F͑v =0͒ state.…”

Section: Introductionmentioning

confidence: 99%

“…Based mainly on energetic considerations, it is likely that the perturber is the upper ͑⍀ =0͒ component of the inverted G 3 ⌸ u ͑v =0͒ state. 22 In order to further characterize these perturbations, we have measured additional PDL-and PDA-based ionization spectra. In Figs.…”

mentioning

confidence: 99%

“…III A 3, with the inclusion of an effective spin-orbit interaction H G͑0͒b͑4͒ between the Table VIII. Unfortunately, these parameters cannot be compared easily with the more precise values of Hashimoto and Kanamori, 22 who employed a different 3 ⌸ Hamiltonian and fitted a greater range of rotational levels. However, the present direct determination of the G-X transition energy is consistent with the sum of the G-E energy of Hashimoto and Kanamori 22 and the E-X energy given by Carroll and Doheny.…”

mentioning

confidence: 99%

“…Unfortunately, these parameters cannot be compared easily with the more precise values of Hashimoto and Kanamori, 22 who employed a different 3 ⌸ Hamiltonian and fitted a greater range of rotational levels. However, the present direct determination of the G-X transition energy is consistent with the sum of the G-E energy of Hashimoto and Kanamori 22 and the E-X energy given by Carroll and Doheny. 49 While the corresponding T 0 values given in Table VIII differ by approximately the combined uncertainties, even this small discrepancy disappears completely if individual low-J energy levels are compared directly, indicating consistency between the energy calibrations of the three relevant works.…”

mentioning

confidence: 99%

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Optical observation of the C, 3sσgF3, and 3pπuG3 Π3u states of N2

Lewis

Baldwin

Sprengers

et al. 2008

The Journal of Chemical Physics

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High-resolution laser-based one extreme-ultraviolet ͑EUV͒ + one UV two-photon ionization spectroscopy and EUV photoabsorption spectroscopy have been employed to study spin-forbidden 3 ⌸ u -X 1 ⌺ g + ͑v ,0͒ transitions in 14 N 2 and 15 N 2 . Levels of the C 3 ⌸ u valence and 3s g F 3 and 3p u G 3 3 ⌸ u Rydberg states are characterized, either through their direct optical observation, or, indirectly, through their perturbative effects on the 1 ⌸ u and 1 ⌺ u + states, which are accessible in dipole-allowed transitions. Optical observation of the G 3 -X͑0,0͒ and ͑1,0͒ transitions is reported for the first time, together with evidence for six new vibrational levels of the C state. Following the recent observation of the F 3 -X͑0,0͒ transition at rotational resolution ͓J. P. Sprengers et al., J. Chem. Phys. 123, 144315 ͑2005͔͒, the F 3 ͑v =1͒ level is found to be responsible for a local perturbation in the rotational predissociation pattern of the bЈ 1 ⌺ u + ͑v =4͒ state. Despite their somewhat fragmentary nature, these new observations provide a valuable database on the 3 ⌸ u states of N 2 and their interactions which will help elucidate the predissociation mechanisms for the nitrogen molecule.

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supporting

confidence: 76%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Optical observation of the C, 3sσgF3, and 3pπuG3 Π3u states of N2

Lewis

Baldwin

Sprengers

et al. 2008

The Journal of Chemical Physics

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Division Xii / Commission 14 / Working Group Collision Processes

Peach¹,

Dimitrijević²,

Stancil³

2008

Proc. IAU

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Research in atomic and molecular collision processes and spectral line broadening has been very active since our last report (Schultz & Stancil 2007, Allard & Peach 2007). Given the large volume of the published literature and the limited space available, we have attempted to identify work most relevant to astrophysics. Since our report is not comprehensive, additional publications can be found in the databases at the web addresses listed in the final section. Elastic and inelastic collisions among electrons, atoms, ions, and molecules are included and reactive processes are also considered, but except for charge exchange, they receive only sparse coverage.

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Diabatic Valence-Hole Concept

Jiang

2024

J. Phys. Chem. A

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A global diabatization scheme, based on the "valence-hole" concept, has been previously applied to model webs of avoided crossings that exist in four electronic-state symmetry manifolds of C 2 ( 1 Π g , 3 Π g , 1 Σ u + , and 3 Σ u + ). Here, this model is extended to the electronically excited states of four more molecules: CN ( 2 Σ + ), N 2 ( 3 Π u ), SiC ( 3 Π), and Si 2 ( 3 Π g ). Many strangenesses in the spectroscopic observations (e.g., energy level structure, predissociation linewidths, and radiative lifetimes) for all four electronic state systems discussed here are accounted for by this unif ied model. The key concept of the model is valence-hole electron configurations: 3σ 2 4σ 1 1π 4 5σ 2 in CN ( 2 Σ + ), 2σ g 2 2σ u 1 1π u 4 3σ g 2 1π g 1 in N 2 ( 3 Π u ), 5σ 2 6σ 1 7σ 2 2π 3 in SiC ( 3 Π), and 4σ g 2 4σ u 1 5σ g 2 2π u 3 in Si 2 ( 3 Π g ), all of which have a triply occupied "valence-core" (i.e., 2σ g 2 2σ u 1 or the equivalent). These valence-hole configurations have a nominal bond order of three or higher and correlate with high-energy separated-atom limits with an np ← ns (n = 2, 3) promotion in one of the atomic constituents. On its way to dissociation, the strongly bound diabatic valence-hole state crosses multiple weakly bound or repulsive states, which belong to electron configurations with a completely filled valence-core. These curve crossings between diabatic potentials result in a network of many avoided crossings among multiple electronic states, analogous to the well-studied electronic structure landscape of ioniccovalent crossings in strongly ionic molecules. Considering the unique role of valence-hole states in shaping the global electronic structure, the valence-hole concept should be added to our intuitive framework of chemical bonding.

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A predissociative triplet Rydberg state of the nitrogen molecule studied by near-infrared diode laser kinetic spectroscopy

Cited by 12 publications

References 16 publications

Optical observation of the C, 3sσgF3, and 3pπuG3 Π3u states of N2

Optical observation of the C, 3sσgF3, and 3pπuG3 Π3u states of N2

Division Xii / Commission 14 / Working Group Collision Processes

Diabatic Valence-Hole Concept

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