Relationship between bond stretching frequencies and internal bonding for [16O4]- and [18O4]phosphates in aqueous solution

Hua Deng, Jianghua Wang, Robert Callender, W. J. Ray

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41 Scopus citations


A normal-mode analysis is used to show that the fundamental stretching frequency, defined as v2 = (vs2 + nava2)/(na + 1) where vs and va are the symmetric and asymmetric modes, respectively, and na the degeneracy of the asymmetric modes, depends almost entirely on the force constant and reduced mass of a P-..O (or P-OH) bond in phosphoric acid or its anions to a good approximation. On the other hand, vs or va, separately, depend not only on these parameters but also on molecular geometry. Thus, P-..O (or P-OH) bond order is more closely related to the fundamental frequency than to the symmetric or asymmetric stretching frequencies. Similar conclusions apply to V-..O (or V-OH) bonds in vanadate molecules. The frequencies for the four different P-..O bonds and three different P-OH bonds in [18O4] phosphoric acid and its three anions were measured by Raman and FT-IR spectroscopy. The measured values, plus those for [16O4] phosphates, were correlated with P-..O valence bond order, by using a modification of the Hardcastle-Wachs procedure (Hardcastle, F. D.; Wachs, I. J. Phys. Chem. 1991, 95, 5031). The bond order/stretching frequency correlations thus produced are expected to hold accurately over a wide range, for both [16O] and [18O] phosphates. Thus, P-..O bond order and bond length in phosphates can be determined from vibrational spectra by using the derived bond order/stretching frequency correlation and the bond length/bond order correlation of Brown and Wu (Acta Crystallogr. 1976, B32, 1957). The accuracy is very high. The error in these relationships is estimated to be within ±0.04 vu and ±0.004 Å for bond orders and bond lengths, respectively, as judged by examining the affects of neglecting small terms in normal-mode analysis and by comparisons of derived bond lengths of P-..O bonds from frequency data to the results from small-molecule crystallographic data.

Original languageEnglish (US)
Pages (from-to)3617-3623
Number of pages7
JournalJournal of Physical Chemistry B
Issue number18
StatePublished - Apr 30 1998

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry


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