Microwave Spectra and Molecular Constants of Arsine and Stibine

Helminger, Paul; Beeson, E. L.; Gordy, Walter

doi:10.1103/physreva.3.122

Cited by 38 publications

(7 citation statements)

References 12 publications

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“…For PH 3 , the PBE and BLYP functionals yield P–H bond lengths of 1.432 and 1.428 Å, respectively, which are slightly longer than the experimental gas-phase value of 1.419 Å, whereas the H–P–H angles of 92.5° and 93.1° for the PBE and BLYP functionals, respectively, are slightly smaller than the experimental gas-phase value of 93.7° . Similar trends are also observed for AsH 3 and SbH 3 , but the deviations in the X–H bond length of 1.550 and 1.745 Å predicted by the PBE functional are somewhat larger compared to the experimental gas-phase values of 1.523 Å and 1.710 Å, respectively, whereas the differences in the H–X–H bending angle are similar (AsH 3 : 90.2° vs 91.34°; SbH 3 : 90.7° vs 91.42°).…”

Section: Results and Discussionsupporting

confidence: 64%

Simulating Vapor–Liquid Equilibria of PH₃, AsH₃, and SbH₃ from First Principles

Chen

Siepmann

2021

J. Phys. Chem. C

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Because of their toxicity, flammability, and chemical instability, the vapor−liquid equilibria of the group V hydrides, phosphine, arsine, and stibine are underexplored. Gibbs ensemble Monte Carlo simulations were performed to obtain the vapor−liquid coexistence curves (VLCCs) for PH 3 , AsH 3 , and SbH 3 by using Kohn−Sham density functional theory with two popular generalized gradient approximation functionals to describe the inter-and intramolecular interactions. In conjunction with the third-generation dispersion correction of Grimme, Goedecker−Teter−Hutter pseudopotentials, and double-ζ valence polarization basis sets, the Perdew−Burke−Ernzerhof (PBE) and Becke−Lee−Yang−Parr (BLYP) exchange-correlation functionals yield critical temperatures for PH 3 of 342 ± 8 and 289 ± 12 K, respectively, that overpredict/underpredict the experimental value by about 20 and 35 K. The high computational cost of first-principles simulations necessitates relatively small system sizes and short simulations that can lead to problems near the critical point. No significant system size effects were observed for the VLCC and liquid structure of PH 3 . For AsH 3 and SbH 3 , the predicted critical temperatures with the PBE exchange-correlation functional are close to 450 K, a value about 20% above the available literature value for AsH 3 .

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Section: Results and Discussionsupporting

confidence: 64%

Simulating Vapor–Liquid Equilibria of PH₃, AsH₃, and SbH₃ from First Principles

Chen

Siepmann

2021

J. Phys. Chem. C

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“…[14][15][16] and references cited therein. The high resolution spectra of the fully deuterated AsD 3 species were analysed in [17][18][19][20][21][22][23]. To the contrary, only surprisingly little information about the spectra of the asymmetric species AsH 2 D and AsHD 2 has been published to present.…”

Section: Introductionmentioning

confidence: 99%

High resolution study of AsHD2: Ground state and the three bending fundamental bands ν3, ν4, and ν6

Ulenikov

Bekhtereva

Bulavenkova

et al. 2006

Journal of Molecular Spectroscopy

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“…The best known molecules with this structure are NH 3 [1] and PH 3 [2]. Room temperature microwave stark-modulated measurements have been made on the arsenic containing molecules, AsF 3 [3] and AsH 3 [4]. Here we present a high-resolution gas-phase microwave study to experimentally determine the B rotational constants, quadrupole coupling, eQq aa and distortion constants for the ground and two excited vibrational states of AsP.…”

Section: Introductionmentioning

confidence: 97%