Polarized infrared spectra of potassium hydrogen maleate and potassium deuterium maleate single crystals

Ilczyszyn, Marek; Baran, J.; Ratajczak, H.; Barnes, Austin J.

doi:10.1016/0022-2860(92)85050-q

Cited by 26 publications

(33 citation statements)

References 24 publications

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“…[35][36][37] The present contribution is related to the previously published work. 12,14,21,[38][39][40][41] The one-dimensional anharmonic vibrational O-H stretching frequency of MPANO, calculated to 1699 cm -1 , is notably lower than the value of 2129 cm -1 obtained in the same way for an unsubstituted analog (picolinic acid N-oxide, PANO). This indicates that the hydrogen bonding of MPANO is stronger than that of PANO, a fact that is reflected in the infrared and NMR experimental findings.…”

Section: D Pes and The Expectation Valuesmentioning

confidence: 69%

Infrared Spectrum of 4-Methoxypicolinic Acid N-Oxide: Computation of Asymmetric O−H Stretching Band

Balazic

Stare

Mavri

2007

J. Chem. Inf. Model.

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In this article we studied the strong intramolecularly hydrogen-bonded system 4-methoxypicolinic acid N-oxide. The potential energy surface V = V(rOH,rOO) and the corresponding dipole moment function were calculated using the DFT B3LYP/6-31+G(d,p) level of approximation. The time-independent vibrational Schrödinger equation was solved using a rectangular grid basis set and shifted Gaussian basis set. The vibrational spectrum and metric parameters were also calculated. Effects of deuteration were considered. The calculated vibrational spectra were compared with the experimental spectra. The vibrational transition corresponding to asymmetric O-H stretching that occurs at about 1400 cm-1 compares well with the experimentally assigned O-H asymmetric stretching band centered at 1380 cm-1. The corresponding asymmetric O-D stretching band was predicted to be at 1154 cm-1, while the experimental O-D band was not assigned due to its very low intensity. Several overtones and hot transitions of significant intensities were located in the vicinity of the fundamental O-H stretching frequency, effectively broadening the infrared absorption attributed to the O-H stretching mode. This is in a good agreement with the observed broad protonic absorptions found in the infrared spectra of the title compound and its analogs. We have shown that the Gaussian basis set is the method of choice for a two-dimensional vibrational problem that requires several hundreds of vibrational basis functions and when high accuracy of the eigenvalues is required or when extending the calculations to more vibrational degrees of freedom. We have also demonstrated that for a large number of basis functions the Gramm-Schmidt orthogonalization procedure outperforms symmetric and canonical orthogonalization schemes.

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Section: D Pes and The Expectation Valuesmentioning

confidence: 69%

Infrared Spectrum of 4-Methoxypicolinic Acid N-Oxide: Computation of Asymmetric O−H Stretching Band

Balazic

Stare

Mavri

2007

J. Chem. Inf. Model.

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“…One of the most investigated systems with a symmetric O/H/O motif is hydrogen maleate ion, that has in the last few decades been thoroughly investigated both experimentally and theoretically. [78][79][80][81][82] This ion is known to have symmetric form both in the gas and in the solid phase, as well as in a solution. The experimental bands of the IR spectrum of potassium hydrogen maleate ion in solution 78 were assigned by gas phase calculations: 79 two modes were found to have predominant OHO asymmetric stretching character, at 540 and at 700 cm À1 .…”

Section: Rsc Advances Papermentioning

confidence: 99%

Intramolecular OHO bonding in dibenzoylmethane: symmetry and spectral manifestations

Petković

Etinski

2014

RSC Adv.

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“…The prototypical intramolecular strong-symmetric hydrogen bond ͑SSHB͒ in the crystal of potassium hydrogen maleate, KH͑OOC u CH v CH u COO͒ or KHM, has been thoroughly investigated with x-ray or neutron diffraction, [25][26][27] infrared and Raman, [28][29][30][31] inelastic neutron scattering ͑INS͒, 27,32-34 NMR, 35,36 and calorimetry. 37 The linear hydrogen bond is very short ͓R OO = 2.427͑1͒ Å at 5 K͔ and crystallographically symmetrical.…”

Section: Introductionmentioning

confidence: 99%

A neutron scattering study of strong-symmetric hydrogen bonds in potassium and cesium hydrogen bistrifluoroacetates: Determination of the crystal structures and of the single-well potentials for protons

Cousson

Archilla

Tomkinson

2008

The Journal of Chemical Physics

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The crystal structures of potassium and cesium bistrifluoroacetates, KH͑CF 3 COO͒ 2 and CsH͑CF 3 COO͒ 2 , respectively, were determined at room and cryogenic temperatures with the single crystal neutron diffraction technique. The crystals belong to the monoclinic space groups, I2 / a and A2 / a, respectively, and there is no evidence of any structural phase transition. In both crystals, trifluoroacetate entities in centrosymmetric dimers are linked by very short hydrogen bonds lying across a center of inversion. The thermal parameters provide no evidence of any double minimum potential for hydrogen bond protons. Single-minimum potentials were determined via best fitting to the inelastic neutron scattering spectral profiles of the stretching vibrations. They comprise a narrow well for the ground state and a very broad quasiharmonic well for excited states. The spread out of the wave functions of these states shows that protons are no longer confined between the oxygens. Presumably, they are attracted by the lone pairs of oxygen atoms. These potentials emphasize the covalent nature of the OO bond and the ionic character of the hydrogen bond proton.

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Polarized infrared spectra of potassium hydrogen maleate and potassium deuterium maleate single crystals

Cited by 26 publications

References 24 publications

Infrared Spectrum of 4-Methoxypicolinic Acid N-Oxide: Computation of Asymmetric O−H Stretching Band

Infrared Spectrum of 4-Methoxypicolinic Acid N-Oxide: Computation of Asymmetric O−H Stretching Band

Intramolecular OHO bonding in dibenzoylmethane: symmetry and spectral manifestations

A neutron scattering study of strong-symmetric hydrogen bonds in potassium and cesium hydrogen bistrifluoroacetates: Determination of the crystal structures and of the single-well potentials for protons

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