Resonance enhanced multiphoton ionization spectroscopy of the NF molecule: 1,3Φ 3d and 4d Rydberg states

S. A. Boggis, J. M. Dyke, A. N. Hughes, T. Keszthelyi, R. Richter, M. Tabrizchi

Research output: Contribution to journalArticle

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Abstract

The (3dδ)1,3Φ and (4dδ)1,3Φ Rydberg states of NF have been investigated by multiphoton ionization (MPI) spectroscopy. These states were observed as two-photon resonances in an overall (2+1) MPI process from NF a1Δ produced from the F+N3 reaction. Ab initio calculations performed at the multireference double excitation configuration interaction level showed that the excited Φ states were of Rydberg character with configurations of ⋯1π 421(3dδ)1 and ⋯1π421(4dδ) 1. The 3Φ←a1Δ two-photon transitions were found to derive their intensities from spin-orbit and spin-uncoupling interactions in the 1Φ3, 3Φ4, 3Φ3, and 3Φ2 upper states. Analysis of the rotationally resolved bands, using a model which includes these factors, allowed the spin-orbit constant, aπ, for the 2π valence orbital to be derived as (159.0±1.0) cm-1. Rotationally resolved envelopes recorded for the (3dδ)1Φ, v′=0, 1←a 1Δ, v″=0 and (3pπ)1Σ+, v′=0←a1Δ, v″=0 (2+1) NF MPI bands, could be simulated reasonably well assuming a Boltzmann rotational distribution for the a1Δ state at ≈180 K. Experiments showed, however, that this was not a true measure of the initial state distribution because of predissociation or perturbation effects in the resonant intermediate state. Assignments for other two-photon resonant NF MPI bands observed in this work are also suggested.

Original languageEnglish
Pages (from-to)1515-1527
Number of pages13
JournalThe Journal of Chemical Physics
Volume102
Issue number4
Publication statusPublished - 1995

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Rydberg states
Ionization
Spectroscopy
ionization
Molecules
Photons
spectroscopy
molecules
photons
Orbits
orbits
Excited states
configuration interaction
excitation
envelopes
valence
orbitals
perturbation
configurations
Experiments

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Boggis, S. A., Dyke, J. M., Hughes, A. N., Keszthelyi, T., Richter, R., & Tabrizchi, M. (1995). Resonance enhanced multiphoton ionization spectroscopy of the NF molecule: 1,3Φ 3d and 4d Rydberg states. The Journal of Chemical Physics, 102(4), 1515-1527.

Resonance enhanced multiphoton ionization spectroscopy of the NF molecule : 1,3Φ 3d and 4d Rydberg states. / Boggis, S. A.; Dyke, J. M.; Hughes, A. N.; Keszthelyi, T.; Richter, R.; Tabrizchi, M.

In: The Journal of Chemical Physics, Vol. 102, No. 4, 1995, p. 1515-1527.

Research output: Contribution to journalArticle

Boggis, SA, Dyke, JM, Hughes, AN, Keszthelyi, T, Richter, R & Tabrizchi, M 1995, 'Resonance enhanced multiphoton ionization spectroscopy of the NF molecule: 1,3Φ 3d and 4d Rydberg states', The Journal of Chemical Physics, vol. 102, no. 4, pp. 1515-1527.
Boggis, S. A. ; Dyke, J. M. ; Hughes, A. N. ; Keszthelyi, T. ; Richter, R. ; Tabrizchi, M. / Resonance enhanced multiphoton ionization spectroscopy of the NF molecule : 1,3Φ 3d and 4d Rydberg states. In: The Journal of Chemical Physics. 1995 ; Vol. 102, No. 4. pp. 1515-1527.
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N2 - The (3dδ)1,3Φ and (4dδ)1,3Φ Rydberg states of NF have been investigated by multiphoton ionization (MPI) spectroscopy. These states were observed as two-photon resonances in an overall (2+1) MPI process from NF a1Δ produced from the F+N3 reaction. Ab initio calculations performed at the multireference double excitation configuration interaction level showed that the excited Φ states were of Rydberg character with configurations of ⋯1π 45σ22π1(3dδ)1 and ⋯1π45σ22π1(4dδ) 1. The 3Φ←a1Δ two-photon transitions were found to derive their intensities from spin-orbit and spin-uncoupling interactions in the 1Φ3, 3Φ4, 3Φ3, and 3Φ2 upper states. Analysis of the rotationally resolved bands, using a model which includes these factors, allowed the spin-orbit constant, aπ, for the 2π valence orbital to be derived as (159.0±1.0) cm-1. Rotationally resolved envelopes recorded for the (3dδ)1Φ, v′=0, 1←a 1Δ, v″=0 and (3pπ)1Σ+, v′=0←a1Δ, v″=0 (2+1) NF MPI bands, could be simulated reasonably well assuming a Boltzmann rotational distribution for the a1Δ state at ≈180 K. Experiments showed, however, that this was not a true measure of the initial state distribution because of predissociation or perturbation effects in the resonant intermediate state. Assignments for other two-photon resonant NF MPI bands observed in this work are also suggested.

AB - The (3dδ)1,3Φ and (4dδ)1,3Φ Rydberg states of NF have been investigated by multiphoton ionization (MPI) spectroscopy. These states were observed as two-photon resonances in an overall (2+1) MPI process from NF a1Δ produced from the F+N3 reaction. Ab initio calculations performed at the multireference double excitation configuration interaction level showed that the excited Φ states were of Rydberg character with configurations of ⋯1π 45σ22π1(3dδ)1 and ⋯1π45σ22π1(4dδ) 1. The 3Φ←a1Δ two-photon transitions were found to derive their intensities from spin-orbit and spin-uncoupling interactions in the 1Φ3, 3Φ4, 3Φ3, and 3Φ2 upper states. Analysis of the rotationally resolved bands, using a model which includes these factors, allowed the spin-orbit constant, aπ, for the 2π valence orbital to be derived as (159.0±1.0) cm-1. Rotationally resolved envelopes recorded for the (3dδ)1Φ, v′=0, 1←a 1Δ, v″=0 and (3pπ)1Σ+, v′=0←a1Δ, v″=0 (2+1) NF MPI bands, could be simulated reasonably well assuming a Boltzmann rotational distribution for the a1Δ state at ≈180 K. Experiments showed, however, that this was not a true measure of the initial state distribution because of predissociation or perturbation effects in the resonant intermediate state. Assignments for other two-photon resonant NF MPI bands observed in this work are also suggested.

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