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

Breidung, J., & Thiel, W. (2019). Equilibrium Structures of the Phosphorus Trihalides PF3 and PCl3, and the Phosphoranes PH3F2, PF5, PCl3F2, and PCl5. The Journal of Physical Chemistry A, 123(26), 5600-5612. doi:10.1021/acs.jpca.9b04406.

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jcc25846-sup-0001-supinfo-1_pub 632.pdf (Supplementary material), 253KB
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jcc25846-sup-0001-supinfo-1_pub 632.pdf
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 Creators:
Breidung, Jürgen1, Author              
Thiel, Walter1, Author              
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1Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              

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 Abstract: 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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Language(s): eng - English
 Dates: 2019-03-092019-06-102019-07-05
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.jpca.9b04406
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Title: The Journal of Physical Chemistry A
  Other : J. Phys. Chem. A
Source Genre: Journal
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Publ. Info: Columbus, OH : American Chemical Society
Pages: - Volume / Issue: 123 (26) Sequence Number: - Start / End Page: 5600 - 5612 Identifier: ISSN: 1089-5639
CoNE: https://pure.mpg.de/cone/journals/resource/954926947766_4