Theoretical modeling of infrared spectra of aspirin and its deuterated derivative

Boczar, Marek; Wójcik, Marek J.; Szczeponek, Krzysztof; Jamroz, D.; Ziȩba, A.; Kawalek, B.

doi:10.1016/s0301-0104(02)00912-6

Cited by 66 publications

(33 citation statements)

References 18 publications

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“…Besides, these values are comparable with those found in our recent work dealing with the H/D isotopic effects in H-bond spectra [21]. However, these ratios are different from those used by Blaise et al, [1] and by Boczar et al [22], because in their approaches, low and high-frequency hydrogen stretching vibrations in individual hydrogen bonds are assumed to be harmonic whereas in the present work we use a Morse potential to describe the anharmonicity of the H-bond bridge. Recall that the removal of the harmonic approximation for the slow modes by introducing Morse potential in place of harmonic one has been done by Leviel and Maréchal [23] in a model similar to the present one, involving cyclic dimer, however, without damping.…”

Section: Table Isupporting

confidence: 91%

Theoretical study of hydrogen and deuterium bond in glutaric acid crystal dimer

Issaoui

Ghalla

Oujia

2011

Int J of Quantum Chemistry

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In the spirit of the work of Blaise et al. [J Chem Phys, 2005, 122, 64306], we have extended their quantum theoretical approach by accounting for the intrinsic anharmonicity of the slow frequency mode, which is described by a Morse potential to reproduce the polarized infrared line shapes of glutaric acid dimer and its deuterium derivative at different temperatures. In this approach, the adiabatic approximation is performed for each separate H-bond bridge of the dimer, and a strong nonadiabatic correction is introduced into the model via the resonant exchange between the fast mode excited states of the two moieties. Working within the strong anharmonic coupling theory, according to which the high-frequency mode is anharmonically coupled to the H-bond bridge, this approach incorporated the Davydov coupling between the excited states of the two moieties, the quantum direct and indirect dampings and the intrinsic anharmonicity of the H-bond bridge. The spectral density was obtained within the linear response theory by Fourier transform of the damped autocorrelation functions. The numerical results show that the theoretical line shapes of the glutaric acid dimer are in fairly good agreement with the experimental ones. Using a minimum number of independent parameters, this theoretical approach fits correctly the experimental line shapes of the glutaric acid dimer. The effects of deuteration and temperature have been successfully reproduced by our calculations.

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Section: Table Isupporting

confidence: 91%

Theoretical study of hydrogen and deuterium bond in glutaric acid crystal dimer

Issaoui

Ghalla

Oujia

2011

Int J of Quantum Chemistry

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“…The corresponding values from X-ray diffraction are also given in the table for comparison. The molecular structure of the 0.975 0.978 C 5 -C 6 -C 7 121.0 120.5 C 6 -C 7 -C 8 -C 9 0.11 0.25 C 2 -C 5 1.519 1.519 C 6 -C 7 -C 8 119.9 119.9 C 7 -C 8 -C 9 -C 10 0.19 0.27 C 5 -C 6 1.401 1.393 C 7 -C 8 -C 9 119.5 119.9 C 8 -C 9 -C 10 -C 5 0.06 0.41 C 6 -C 7 1.395 1.383 C 8 -C 9 -C 10 120.4 120.1 C 9 -C 10 -C 5 -C 6 0.17 0.54 C 7 -C 8 1.394 1.379 C 9 -C 10 -C 5 120.4 120.1 C 2 -C 5 -C 6 -H 6 3.1 6.5 C 8 -C 9 1.395 1.395 C 5 -C 6 -H 6 119.4 119.5 C 5 -C 6 -C 7 -H 7 179.8 172.9 C 9 -C 10 1.394 1.382 C 6 -C 7 -H 7 119.7 117.8 C 6 -C 7 -C 8 -H 9 179.8 176.0 C 10 -C 5 1.402 1.397 C 7 -C 8 -H 9 120.2 121.9 C 7 -C 8 -C 9 -H 9 179.5 177.4 C 6 -H 6 1.088 0.933 C 8 -C 9 -H 10 120.0 126.9 C 8 -C 9 -C 10 -H 10 178.8 177.3 C 7 -H 7 1.086 1.027 C 9 -C 10 -H 11 119.8 115.6 C 8 -H 9 1.086 1.077 C 9 -H 9 1.086 0.956 C 10 -H 10 1.086 0.996 compound with the atom numbering scheme adopted in the computations is shown in Fig. 3.…”

Section: Crystallographic and Molecular Structuresmentioning

confidence: 99%

Dimerisation and vibrational spectroscopic properties of (RS)-phenylsuccinic acid

Sajan¹,

Fischer

Joe³

et al. 2006

J. Raman Spectrosc.

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Single crystals of (RS)-phenylsuccinic acid (RSPSA) were grown by the slow evaporation technique and vibrational spectral analysis was carried out using near-IR Fourier transform Raman and Fourier transform IR spectroscopy. The density functional theoretical (DFT) computations were also performed at the B3LYP/6-31G(d) level to derive the equilibrium geometry, vibrational wavenumbers, intensities and atomic charges. Vibrational spectral investigation confirmed the formation of cyclic dimers in the crystal, with the carboxyl groups of each acid molecule being hydrogen bonded to those of the adjacent molecules. Each molecule is connected to two other molecules, forming infinite chains. The wavenumber difference observed between the carbonyl modes in the IR and Raman spectra might be attributed to the intramolecular association based on C O· · ·H type hydrogen bonding in the molecule. In a hydrogenbonded carbonyl, resonance can occur, which places a partial negative charge on the oxygen atom accepting the hydrogen bond and a positive charge on the atom donating the hydrogen. The resulting partial 'transfer of allegiance' of the proton enhances resonance and lowers the carbonyl stretching wavenumber. The O-H stretching vibrational wavenumber is red-shifted owing to the formation of strong O-H· · ·O hydrogen bonds by hyperconjugation between carbonyl oxygen lone electron pairs and O-H s * antibonding orbitals. Vibrational analysis was used to investigate the C-H· · ·O interaction and electronic effects, induction of the methylene group by an adjacent electronegative atom and the resulting increase of stretching mode wavenumbers and decrease of infrared intensities.

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“…The parameters used in subsequent calculations of the energy splittings have been calculated from the results of the B3LYP/6-311++G** data and are listed in Table 4. The parameter α describing coupling between the O-H stretching mode ν 73 and the mode ν 4 , ν 7 , ν 8 , ν 11 , ν 13 or ν 16 represent an analogue of linear distortion parameters b used for theoretical reproduction of the X-H infrared band shapes of tropolone [34], salicylaldehyde [35] or aspirin [36]. Both different spectroscopic facts thus have the same origin, the anharmonic coupling in the potential energy between the two X-H and X...Y vibrations.…”

Section: Model Calculationsmentioning

confidence: 99%