Structure, bonding, and internal rotation in H3PO, H2POH, and HFPOH

Michael W. Schmidt, Satoshi Yabushita, Mark S. Gordon

Research output: Contribution to journalArticle

75 Citations (Scopus)

Abstract

The fundamental nature of the PO bond is reexamined by using ab initio (3-21G* and 6-31G*) wave functions and energy-localized orbitals. The bond is best described as a dative single bond augmented by π back-donation from the oxygen lone pairs. The isomerization pathway from H3PO to H2POH is followed by using the intrinsic reaction coordinate and localized orbitals. The latter, more stable, isomer has two forms, cis and trans, which are nearly equal in energy. The internal rotation barriers in this molecule and in HFPOH are examined with a Fourier analysis and compared with their nitrogen analogues. The major differences between the potential curves in phosphorus and nitrogen species are attributed to different dipole-dipole (DD) interactions between the HYX and OH moieties.

Original languageEnglish
Pages (from-to)382-389
Number of pages8
JournalJournal of Physical Chemistry
Volume88
Issue number3
Publication statusPublished - 1984
Externally publishedYes

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Nitrogen
dipoles
nitrogen
orbitals
Fourier analysis
Wave functions
Isomerization
Isomers
Phosphorus
isomerization
phosphorus
isomers
wave functions
analogs
Oxygen
Molecules
energy
oxygen
curves
molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Structure, bonding, and internal rotation in H3PO, H2POH, and HFPOH. / Schmidt, Michael W.; Yabushita, Satoshi; Gordon, Mark S.

In: Journal of Physical Chemistry, Vol. 88, No. 3, 1984, p. 382-389.

Research output: Contribution to journalArticle

Schmidt, Michael W. ; Yabushita, Satoshi ; Gordon, Mark S. / Structure, bonding, and internal rotation in H3PO, H2POH, and HFPOH. In: Journal of Physical Chemistry. 1984 ; Vol. 88, No. 3. pp. 382-389.
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