Zum Schwingungsspektrum der Phosphorsäure. I. Infrarot‐ und RAMAN‐Spektren von Phosphatlösungen

Steger, E.; Herzog, K.

doi:10.1002/zaac.19643310308

Cited by 81 publications

(37 citation statements)

References 17 publications

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“…The experimental vibrational spectrum of aqueous H 2 PO 4 2Ϫ has also been reported [33][34][35]. Calculations of the symmetric stretch for H 2 PO 4 Ϫ at 1,084 cm Ϫ1 are in good agreement with the assignment for the peak observed at 1,075 cm Ϫ1 and the asymmetric PϭO harmonic stretch calculated at 1,305 is in reasonable agreement with the anharmonic experimental value at 1,240 cm Ϫ1 .…”

Section: Resultssupporting

confidence: 79%

Accurate heats of formation and acidities for H₃PO₄, H₂SO₄, and H₂CO₃ from ab initio electronic structure calculations

Alexeev

Windus

Chen

et al. 2004

Int J of Quantum Chemistry

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Ϫ were calculated using coupled cluster theory including noniterative, quasi-perturbative triple excitations (CCSD(T)) with large basis sets. Optimized geometries and harmonic vibrational frequencies were calculated at the MP2/aug-cc-pVTZ level. Atomization energies were obtained by extrapolating CCSD(T) valence energies to the complete basis set limit (CBS) using the aug-cc-pV(nϩd)Z (n ϭ D, T, Q) basis sets where the ϩd corresponds to the inclusion of tight d functions for the second row atoms P and S. In order to achieve near chemical accuracy (Ϯ1 kcal/ mol) in the thermodynamic properties, a core/valence correction, a Douglas-Kroll-Hess scalar relativistic correction, and a first-order atomic spin-orbit correction were included. The calculated heats of formation of the neutral molecules at 0 K are are in good agreement with the respective experimental values of 323.0 Ϯ 4.9 and 302.3 Ϯ 2.6 kcal/mol. Solution acidities are computed using the fully polarizable continuum model. Using an electron density contour value of 0.001 a.u. to define the cavity for the neutral molecules and of 0.0022 a.u. for the anions, we calculate pK a (H 2 CO 3 ) ϭ 6.3, pK a (H 3 PO 4 ) ϭ 2.5, and pK a (HNO 3 ) ϭ -2.4 which are within one pK a of the respective experimental values of 6.4, 2.1, and -1.4. We predict the pK a of H 2 SO 4 in aqueous solution to be in the range of -6 to -8, significantly lower than the estimated experimental values in the range of -3.

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Section: Resultssupporting

confidence: 79%

Accurate heats of formation and acidities for H₃PO₄, H₂SO₄, and H₂CO₃ from ab initio electronic structure calculations

Alexeev

Windus

Chen

et al. 2004

Int J of Quantum Chemistry

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“…with the literature, [27][28][29][30] we assign the bands at 880 and 940 cm −1 to the symmetric and asymmetric P-(OH) 2 stretching vibrations. The bands at 1080 and 1160 cm −1 are assigned to the symmetric and asymmetric PO − 2 stretching vibrations (ν S (PO − 2 ) and ν AS (PO − 2 )) with distinctly different linewidths, and the shoulder around 1250 cm −1 to the P-(OH) 2 bending vibrations (δ S (P-(OH) 2 ) and δ AS (P-(OH) 2 )).…”

Section: Introductionsupporting

confidence: 78%

Ultrafast phosphate hydration dynamics in bulk H2O

Costard

Tyborski

Fingerhut

et al. 2015

The Journal of Chemical Physics

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Phosphate vibrations serve as local probes of hydrogen bonding and structural fluctuations of hydration shells around ions. Interactions of H2PO4− ions and their aqueous environment are studied combining femtosecond 2D infrared spectroscopy, ab-initio calculations, and hybrid quantum-classical molecular dynamics (MD) simulations. Two-dimensional infrared spectra of the symmetric (νS(PO2−)) and asymmetric (νAS(PO2−)) PO2− stretching vibrations display nearly homogeneous lineshapes and pronounced anharmonic couplings between the two modes and with the δ(P-(OH)2) bending modes. The frequency-time correlation function derived from the 2D spectra consists of a predominant 50 fs decay and a weak constant component accounting for a residual inhomogeneous broadening. MD simulations show that the fluctuating electric field of the aqueous environment induces strong fluctuations of the νS(PO2−) and νAS(PO2−) transition frequencies with larger frequency excursions for νAS(PO2−). The calculated frequency-time correlation function is in good agreement with the experiment. The ν(PO2−) frequencies are mainly determined by polarization contributions induced by electrostatic phosphate-water interactions. H2PO4−/H2O cluster calculations reveal substantial frequency shifts and mode mixing with increasing hydration. Predicted phosphate-water hydrogen bond (HB) lifetimes have values on the order of 10 ps, substantially longer than water-water HB lifetimes. The ultrafast phosphate-water interactions observed here are in marked contrast to hydration dynamics of phospholipids where a quasi-static inhomogeneous broadening of phosphate vibrations suggests minor structural fluctuations of interfacial water.

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“…For the free P043-ion (T, symmetry) there are four normal modes of vibration, all of which are Raman active whereas only v3 and v4 are infrared active (25). These two bands are observed at 1017 and 567 cm-l, respectively, in P043- (26). In the infrared spectrum of (Me3Sn)3P04 three strong bands are observed in the PO4 stretching region Can.…”

Section: Tris(trimethy1tin) Orthophosphatementioning

confidence: 98%

The synthesis, Mössbauer and vibrational spectra of some triorganotin derivatives of phosphorus oxyacids

Chivers¹,

Roode²,

Ruddick³

et al. 1976

Can. J. Chem.

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Trimethyltin hypophosphite, Me3SnPO2H2, bis(trimethyltin) phosphite dihydrate, (Me3Sn)2PO3H.2H2O, and bis(triphenyltin) phosphite, (Ph3Sn)2PO3H, have been obtained from the organotin chloride and aqueous solutions of the sodium salt of the corresponding phosphorus oxy-acid. (Me3Sn)2PO3H.2H2O can be dehydrated under vacuum at 25 °C, but disproportionation occurs on heating. Tris(trimethyltin) orthophosphate, (Me3Sn)3PO4, was prepared from trimethyltin chloride and silver phosphate in methanol and gave an adduct formulated as [Formula: see text] after recrystallization from 1,4-dioxane. Vibrational spectra and Mössbauer data for Me3SnPO2H2 are consistent with a trigonal bipyramidal structure in which planar Me3Sn groups are bridged symmetrically by PO2H2 groups. The Mössbauer spectra of (Me3Sn)2PO3H, (Ph3Sn)2PO3H, and (Me3Sn)2PO3H.2H2O suggest that the two tin atoms are in similar (probably pentacoordinate) environments, implying at least one three coordinate oxygen per formula unit. For (Me3Sn)3PO4, the vibrational spectra, Mössbauer data, and physical properties are consistent with a weakly associated structure in which all three tin atoms are in similar environments. It is suggested that association is achieved via the phosphoryl (P=O) oxygen atom, which is weakly coordinated to three tin atoms leading to a distortion of the tetrahedral arrangement around tin towards trigonal bipyramidal.

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Zum Schwingungsspektrum der Phosphorsäure. I. Infrarot‐ und RAMAN‐Spektren von Phosphatlösungen

Cited by 81 publications

References 17 publications

Accurate heats of formation and acidities for H₃PO₄, H₂SO₄, and H₂CO₃ from ab initio electronic structure calculations

Accurate heats of formation and acidities for H₃PO₄, H₂SO₄, and H₂CO₃ from ab initio electronic structure calculations

Ultrafast phosphate hydration dynamics in bulk H2O

The synthesis, Mössbauer and vibrational spectra of some triorganotin derivatives of phosphorus oxyacids

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Zum Schwingungsspektrum der Phosphorsäure. I. Infrarot‐ und RAMAN‐Spektren von Phosphatlösungen

Cited by 81 publications

References 17 publications

Accurate heats of formation and acidities for H3PO4, H2SO4, and H2CO3 from ab initio electronic structure calculations

Accurate heats of formation and acidities for H3PO4, H2SO4, and H2CO3 from ab initio electronic structure calculations

Ultrafast phosphate hydration dynamics in bulk H2O

The synthesis, Mössbauer and vibrational spectra of some triorganotin derivatives of phosphorus oxyacids

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Accurate heats of formation and acidities for H₃PO₄, H₂SO₄, and H₂CO₃ from ab initio electronic structure calculations

Accurate heats of formation and acidities for H₃PO₄, H₂SO₄, and H₂CO₃ from ab initio electronic structure calculations