THE b1Σ+–X3Σ− BAND SYSTEM OF NF

The microwave absorption spectrum of the PF radical in the X 3~ -state was detected by using a source modulation microwave spectrometer. The radical was produced in a free space cell by a dc glow discharge in a mixture of PH 3 and CF 4 , Five rotational transitions with N = 1 +-0 up to 5 +-4 were observed in the frequency region of 44 to 171 GHz and were least-squares analyzed to determine the rotational constant, the centrifugal distortion constant, the spin-spin coupling constant with its centrifugal distortion term, the spin-rotation coupling constant, and the magnetic hyperfine coupling constants for both phosphorus and fluorine nuclei. A centrifugal correction term was found to be necessary for the c magnetic hyperfine constant of phosphorus in order to achieve a good fitting of the observed spectrum. The present data agree with, but considerably improve the accuracies of ground-state molecular constants which Douglas and Frackowiak derived from high-resolution emission spectra. The spin density and the s character of the unpaired-electron orbital were calculated from the observed magnetic hyperfine coupling constants to be 91.3% and 0.88% for P and 9.1 % and 0.17% for F.

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“…The observed spectrum was analyzed using the following Hamiltonian: (2) and H hfs = b{P)I(P). S + c(P)IAP)Sz…”

Section: Discussionmentioning

confidence: 99%

The microwave spectrum of the PF radical in the ground X 3Σ− electronic state

Saito

Endo

Hirota

1985

The Journal of Chemical Physics

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“…It is extremely likely that the band observed at 525 nm (Fig 2a) is that identified by Douglas and Jones [17], and assigned to NF Bettendorrff and Peyerimoff [28] have predicted that the higher states of NF are all repulsive.…”

Section: Discussionmentioning

confidence: 73%

“…The values were calculated from 0 K heats of formation taken from the JANAF tables [32]. The energies of the NF b 1 Σ + and F 2 A 1 Π u states are taken from Douglas and Jones [17], and Huber and Herzberg [33], respectively.…”

Section: Energetics Of the Key Dissociation Channelsmentioning

confidence: 99%

The observation of fluorescence from excited states of NF2 and NF following the photodissociation of NF3 in the 11–30 eV range

Seccombe

Tuckett

Jochims

et al. 2001

Chemical Physics Letters

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A study of the vacuum-ultraviolet (VUV) fluorescence spectroscopy of NF 3 in the 11-30 eV range is presented. Synchrotron radiation from BESSY1, Berlin provides the VUV excitation source. Emission due to NF bΣ -at 528.8 nm is observed between 11.5 and 21.0 eV.Other emissions, which are believed to be due to transitions between highly excited states of NF 2 , are observed at higher energies, 14.8-24.5 eV. Lifetimes associated with two of these bands at 325 nm and 410 nm are determined to be 12.9 and 13.0 ns, respectively. The similarity of the measured values implies that the two transitions originate from a common upper state. Seccombe et al. (2001) 3

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“…For example, in the NF b I};+ state Be is 1.2377 cm-I . 24 Rydberg states with a NF+ (X 2II) core are expected to have very similar spectroscopic constants to the ground ionic state. Hence MPI spectra from the X, a, or b states to Rydberg states of this type should show vibronic bands which are blue degraded.…”

Section: Resultsmentioning

confidence: 99%

“…[24][25][26] Diode laser abtant as a means of detecting and characterizing short-lived reaction intermediates in the gas phase. 1 ,2 As multiphoton sorption studies 27 and electron paramagnetic resonance selection rules are more relaxed than single photon selec-(EPR) and laser magnetic resonance (LMR) investigation rules, the technique has permitted the characterization tions 28 ,29 have also been made.…”

Section: Introductionmentioning

confidence: 99%

Resonance enhanced multiphoton ionization spectroscopy of the NF molecule: 1Σ+ and 1Δ 3p Rydberg states

Dyke

Keszthelyi

Lee

et al. 1993

The Journal of Chemical Physics

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Resonance enhanced multiphoton ionization spectroscopy of the NF molecule: 1,3Φ 3d and 4d Rydberg states J. Chem. Phys. 102, 1515 (1995; 10.1063/1.468884 (3+1) resonance enhanced multiphoton ionization photoelectron spectroscopy on nf Rydberg states of carbon dioxide J. Chem. Phys. 101, 9303 (1994); 10.1063/1.467961 Polarizationresolved (2+1) resonanceenhanced multiphoton ionization spectroscopy of CF3I (6s) Rydberg states J. Chem. Phys. 98, 4355 (1993); 10.1063/1.464997Spectroscopy of the 3p 2Π Rydberg state of HCO by resonanceenhanced multiphoton ionization Two Rydberg states of the NF molecule, the 2 III and 2 1 ~ + states, have been investigated by multiphoton ionization (MPI) spectroscopy. These states are observed Via the two-photon resonance enhancements they provide in the multiphoton ionization spectra of NF a III and NF b 1 ~ +. Both states are assigned on the basis of experimerital evidence as Rydberg states with the dominant configuration ... l1r 4 Sa221T 1 (3p1T) 1. Ab initio calculations performed at the multireference determinant configuration interaction (MRDCI) level showed that these states were of mixed Rydberg-valence character with the Rydberg character [ ... I1T 4 Sa221Tl (3p1T) 1] dominating at short bond lengths ( < 1.3S A) and the valence character ( ... I1T 3 Sa221T 3 ) becoming more important at longer bond lengths (> 1.35 A). These calculations also proved useful in providing a mechanism to account for the rotational predissociation observed in the experimental spectra.

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THE b¹Σ⁺–X³Σ⁻ BAND SYSTEM OF NF

Cited by 96 publications

References 7 publications

The microwave spectrum of the PF radical in the ground X 3Σ− electronic state

The microwave spectrum of the PF radical in the ground X 3Σ− electronic state

The observation of fluorescence from excited states of NF2 and NF following the photodissociation of NF3 in the 11–30 eV range

Resonance enhanced multiphoton ionization spectroscopy of the NF molecule: 1Σ+ and 1Δ 3p Rydberg states

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