The b1Σ+-X3Σ− band system of PF

Colin, Réginald; Devillers, Jean-Jacques; Prevot, F.

doi:10.1016/0022-2852(72)90102-6

Cited by 26 publications

(3 citation statements)

References 11 publications

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“…The first excited valence states ͑A 3 ⌸ and d 1 ⌸͒ both arise from the electron configuration 4 1 * 3 , whilst the next excited bound singlet state, g 1 ⌸, is probably a Rydberg state. The A -X, d -a, d -b, g -a, and g -b transitions were first characterized in emission at rotational resolution by Douglas and Frackowiak, 14 and the energies of the singlet relative to the triplet states were determined by observation of the spin-forbidden b -X transition at 748 nm by Colin et al 30 The radiative lifetimes of the A 3 ⌸, b 1 ⌺ ϩ , and d 1 ⌸ states have recently been measured by Setser et al 31,32 Figure 1 shows four fluorescence excitation spectra of PF 3 recorded between 9-20 eV at Daresbury with an optical resolution of 0.1 nm. In Fig.…”

Section: Andmentioning

confidence: 99%

Vacuum-UV fluorescence spectroscopy of PF3 in the range 9–20 eV

Biehl

Boyle

Seccombe

et al. 1998

The Journal of Chemical Physics

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The vacuum-UV and visible spectroscopy of PF 3 using fluorescence excitation and dispersed emission techniques is reported. The fluorescence excitation spectrum has been recorded following photoexcitation with monochromatized synchrotron radiation from the Daresbury, UK source in the energy range 9-20 eV with an average resolution of ϳ0.015 eV. Transitions to the three lowest-energy bands in the Rydberg spectra show resolved vibrational structure, they are assigned to transitions to the (8a 1) Ϫ1 4p, 5p, and 6p Rydberg states of PF 3 , and fluorescence is due to valence transitions in the PF 2 radical. From a Franck-Condon analysis of the vibrational structure, it is shown that the FPF bond angle in PF 3 increases by ϳ14Ϯ1°upon photoexcitation. The use of optical filters shows that at least three excited electronic states of PF 2 are responsible for the induced emission. Dispersed emission spectra in the UV/visible region have been recorded with an optical resolution of 8 nm at the BESSY 1, Germany synchrotron source at the energies of all the peaks in the excitation spectrum. Four different decay channels are observed: ͑a͒ PF 2 Ã 2 A 1-X 2 B 1 fluorescence in the wide range 320-550 nm for photon energies around 9.8 eV, ͑b͒ PF 2 Ã-X, and B 2 B 2-X 2 B 1 fluorescence at ϳ300 nm for photon energies around 11.0 eV, ͑c͒ PF 2 C 2 A 1-X 2 B 1 and Ẽ 2 B 1 (2 ⌸)-Ã 2 A 1 fluorescence at ϳ222 and 325 nm, respectively, for photon energies around 14.4 eV, and ͑d͒ PF A 3 ⌸-X 3 ⌺ Ϫ fluorescence between 300-380 nm for photon energies around 16.1 eV. These assignments are confirmed by action spectra in which the excitation energy of the vacuum-UV radiation is scanned with detection of the fluorescence at a fixed, dispersive wavelength. Using the single-bunch mode of the BESSY 1 source, we have attempted to measure the lifetimes of the emitting states, but the timing profile of the source imposes an upper limit on lifetimes that can be measured of ϳ500 ns. We have therefore only been able to measure values for the bent C 2 A 1 and linear Ẽ 2 B 1 (2 ⌸) states of PF 2 of 14.7 and 7.9 ns, respectively; the lifetimes of the other emitters are too long to measure by this method. Our assignments in PF 2 are heavily dependent on recent ab initio calculations on the geometries and energies of the valence electronic states of this species. Our knowledge on the electronic spectroscopy of this free radical is reviewed.

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Section: Andmentioning

confidence: 99%

Vacuum-UV fluorescence spectroscopy of PF3 in the range 9–20 eV

Biehl

Boyle

Seccombe

et al. 1998

The Journal of Chemical Physics

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“…12 Notably, both NF and PF species are valence isoelectronic with the O 2 molecule with triplet ground state and have been investigated experimentally as well as theoretically 39. 40…”

Section: Introductionmentioning

confidence: 99%

Prediction of a Neutral Noble Gas Compound in the Triplet State

Manna

Ghosh

Ghanty

2015

Chemistry A European J

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Discovery of the HArF molecule associated with H-Ar covalent bonding [Nature, 2000, 406, 874-876] has revolutionized the field of noble gas chemistry. In general, this class of noble gas compound involving conventional chemical bonds exists as closed-shell species in a singlet electronic state. For the first time, in a bid to predict neutral noble gas chemical compounds in their triplet electronic state, we have carried out a systematic investigation of xenon inserted FN and FP species by using quantum chemical calculations with density functional theory and various post-Hartree-Fock-based correlated methods, including the multireference configuration interaction technique. The FXeP and FXeN species are predicted to be stable by all the computational methods employed in the present work, such as density functional theory (DFT), second-order Møller-Plesset perturbation theory (MP2), coupled-cluster theory (CCSD(T)), and multireference configuration interaction (MRCI). For the purpose of comparison we have also included the Kr-inserted compounds of FN and FP species. Geometrical parameters, dissociation energies, transition-state barrier heights, atomic charge distributions, vibrational frequency data, and atoms-in-molecules properties clearly indicate that it is possible to experimentally realize the most stable state of FXeP and FXeN molecules, which is triplet in nature, through the matrix isolation technique under cryogenic conditions.

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“…In the case of the d state, however, no vibrational dependence of radiative lifetime was identified. The relative positioning of the singlet and triplet manifolds was established by Colin et al 25 who observed the spin forbidden b 1 ⌺ ϩ -X 3 ⌺ Ϫ transition.…”

Section: Introductionmentioning

confidence: 90%

An injection seeded narrow bandwidth pulsed optical parametric oscillator and its application to the investigation of hyperfine structure in the PF radical

Chekhlov

Elks

Western

et al. 2001

The Journal of Chemical Physics

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We describe the construction of an all solid-state, narrow bandwidth, pulsed optical parametric oscillator (OPO) based on ß-barium borate nonlinear crystals. The OPO was injection seeded by an external cavity diode laser in the range 755–855 nm to generate high power narrow bandwidth tunable light in this range and simultaneously at 606–669 nm. The bandwidth of the visible light was ~130 MHz, and after frequency doubling or sum frequency mixing with the second harmonic of the pump Nd:YAG laser, sub-Doppler spectra with an overall resolution of 450 MHz were taken in the UV. The system is demonstrated by taking high-resolution spectra of the v' = 2–3 and 5–7 bands of the A?3?–X?3S-(v',0) progression and the v' = 4–v? = 0 band of the d?1?–a?1? transition in PF. These spectra show clear hyperfine structure, and an analysis of this structure is presented and interpreted in terms of the electronic structure of the molecule. As a prelude to this high-resolution study, the first ten members of the A–X band system and the first five members of the d–a band system were recorded at the moderate resolution provided by a pulsed dye laser

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The b1Σ+-X3Σ− band system of PF

Cited by 26 publications

References 11 publications

Vacuum-UV fluorescence spectroscopy of PF3 in the range 9–20 eV

Vacuum-UV fluorescence spectroscopy of PF3 in the range 9–20 eV

Prediction of a Neutral Noble Gas Compound in the Triplet State

An injection seeded narrow bandwidth pulsed optical parametric oscillator and its application to the investigation of hyperfine structure in the PF radical

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