Pure rotational spectrum of phosphorus pentafluoride observed by microwave Fourier transform spectroscopy

Styger, C.; Bauder, A.

doi:10.1016/0022-2852(91)90403-w

Cited by 14 publications

(11 citation statements)

References 31 publications

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“…To be more specific, we utilized for the asymmetric top species PX 2 (X = H, D, F) the measured 67−69 constants A 0 , B 0 , and C 0 , and for the oblate symmetric top molecules PH 3 , PD 3 , and PF 3 the B 0 and C 0 constants, 70−72 which refer to the so-called B-reduction of the rotational Hamiltonian for PH 3 and PD 3 . 70,71 Furthermore, we used the B 0 constants 5,6 of the P 35 Cl 3 and P 37 Cl 3 isotopologues, as well as the published 7,8,11,12 A 0 and B 0 constants for the prolate symmetric tops PH 3 F 2 and PF 5 . In order to deduce the equilibrium rotational constants, the corresponding zeropoint vibrational corrections 13,73,74 ΔX vib (X = A, B, C) are needed.…”

Section: Methodsmentioning

confidence: 99%

Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅

Breidung

Thiel

2019

J. Phys. Chem. A

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Among the title species, a reliable and accurate equilibrium geometry (re structure) is available only for PF3, which has been determined experimentally more than 20 years ago. Here, we report accurate re structures for all title molecules, which were obtained using a composite computational approach based on explicitly correlated coupled-cluster theory (CCSD(T)-F12b) in conjunction with a large correlation-consistent basis set (cc-pCVQZ-F12) to take core–valence electron correlation into account. Additional terms were included to correct for the effects of iterative triple excitations (CCSDT), noniterative quadruple excitations (CCSDT(Q)), and scalar relativistic contributions (DKH2-CCSD(T)). The performance of this computational procedure was established through test calculations on selected small molecules (PH, PF, PCl, PH2, PF2, and PH3). For PF3, PCl3, PH3F2, and PF5 sufficiently accurate experimental ground-state rotational constants from the literature were used to determine semiexperimental re structures, which were found to be in excellent agreement with the corresponding best estimates from the current composite approach. The recommended equilibrium structural parameters are for PCl3, re(PCl) = 203.94 pm and θe(ClPCl) = 100.18°; for PH3F2, re(PHeq) = 138.38 pm and re(PFax) = 164.15 pm; for PF5, re(PFeq) = 153.10 pm and re(PFax) = 157.14 pm; for PCl3F2, re(PCleq) = 200.21 pm and re(PFax) = 159.37 pm; and for PCl5, re(PCleq) = 201.29 pm and re(PClax) = 211.83 pm. The associated uncertainties are estimated to be ±0.10 pm and ±0.10°, respectively.

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Section: Methodsmentioning

confidence: 99%

Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅

Breidung

Thiel

2019

J. Phys. Chem. A

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“…The spectrometer design and operation have been described previously (10,29). The measurement conditions were similar to those used for OPF 3 (9) and PF 5 (11). Here only a brief summary will be given of the relevant details.…”

Section: Experimental Methodsmentioning

confidence: 99%

“…[6] above is written by these authors without the prime; see the last term in their Eq. [11]. The Hamiltonian in Eq.…”

Section: Ii1 the Effective Hamiltonianmentioning

confidence: 99%

“…The direct channel is clear from Eqs. [10] and [11] where the (⌬k ϭ Ϯ3) and the (⌬k ϭ Ϯ6) overlap sums appear. For (v 6 ϭ 0), one can require these sums to approach ϩ1 (rather than Ϫ1) in the limit of infinite barrier height, so that the matrix elements go over into their C 3v form, as they must.…”

Section: Appendix: the Phase Of The Torsional Wave Functionsmentioning

confidence: 99%

“…The selection rules are ⌬J ϭ 0, Ϯ1; ⌬k ϭ Ϯ3; ⌬ ϭ 0. This method has been used to measure "forbidden" rotational energy differences in symmetric rotors without internal rotation, both for polar molecules such as PH 3 (7) and OPF 3 (8,9), and for non-polar systems such as BF 3 (10), PF 5 (11), and SO 3 (12). However, studies of internal rotation in symmetric rotors have not (to our knowledge) been previously published.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

The Forbidden RotationalQ-Branch of CH3CF3: Torsional Properties and (A1−A2) Splittings

Ozier

Schroderus

Wang

et al. 1998

Journal of Molecular Spectroscopy

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Fundamentals of Rotational Spectroscopy

Bauder

2011

Handbook of High‐resolution Spectroscopy

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Essential features of rotational spectra are developed on the basis of the quantum mechanics of molecular rotation. The effects of the harmonic vibrations of the nuclei are considered on the molecular rotation. Permanent electric dipole moments are required for the observation of pure rotational transitions. The Stark effect is used to determine the electric dipole moment. Nuclear quadrupole splittings give information on the electronic charge distribution in molecules. Large‐amplitude internal motions in molecules lead to splittings of rotational transitions. The splittings determine the potential barriers of the internal motions.

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Pure rotational spectrum of phosphorus pentafluoride observed by microwave Fourier transform spectroscopy

Cited by 14 publications

References 31 publications

Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅

Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅

The Forbidden RotationalQ-Branch of CH3CF3: Torsional Properties and (A1−A2) Splittings

Fundamentals of Rotational Spectroscopy

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Pure rotational spectrum of phosphorus pentafluoride observed by microwave Fourier transform spectroscopy

Cited by 14 publications

References 31 publications

Equilibrium Structures of the Phosphorus Trihalides PF3 and PCl3, and the Phosphoranes PH3F2, PF5, PCl3F2, and PCl5

Equilibrium Structures of the Phosphorus Trihalides PF3 and PCl3, and the Phosphoranes PH3F2, PF5, PCl3F2, and PCl5

The Forbidden RotationalQ-Branch of CH3CF3: Torsional Properties and (A1−A2) Splittings

Fundamentals of Rotational Spectroscopy

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Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅

Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅