Catalytic Sulfation of Betulin with Sulfamic Acid: Experiment and DFT Calculation.

Betulin is an important triterpenoid substance isolated from birch bark, which, together with its sulfates, exhibits important bioactive properties. We report on a newly developed method of betulin sulfation with sulfamic acid in pyridine in the presence of an Amberlyst®15 solid acid catalyst. It has been shown that this catalyst remains stable when being repeatedly (up to four cycles) used and ensures obtaining of sulfated betulin with a sulfur content of ~10%. The introduction of the sulfate group into the betulin molecule has been proven by Fourier-transform infrared, ultraviolet-visible, and nuclear magnetic resonance spectroscopy. The Fourier-transform infrared (FTIR) spectra contain absorption bands at 1249 and 835-841 cm-1; in the UV spectra, the peak intensity decreases; and, in the nuclear magnetic resonance (NMR) spectra, of betulin disulfate, carbons С3 and С28 are completely shifted to the weak-field region (to 88.21 and 67.32 ppm, respectively) with respect to betulin. Using the potentiometric titration method, the product of acidity constants K1 and K2 of a solution of the betulin disulfate H+ form has been found to be 3.86 × 10-6 ± 0.004. It has been demonstrated by the thermal analysis that betulin and the betulin disulfate sodium salt are stable at temperatures of up to 240 and 220 °C, respectively. The density functional theory method has been used to obtain data on the most stable conformations, molecular electrostatic potential, frontier molecular orbitals, and mulliken atomic charges of betulin and betulin disulfate and to calculate the spectral characteristics of initial and sulfated betulin, which agree well with the experimental data.

Theoretical Study of Proton Tunneling in the Imidazole-Imidazolium Complex.

Proton tunneling in the hydrogen-bonded imidazole-imidazolium complex ion has been studied theoretically. Ab initio CASSCF/6-311++G(d,p) calculations concerning geometry optimization and vibrational frequencies have been carried out for equilibrium and transition state structures of the system. Two-dimensional double-well model potentials were constructed on the basis of ab initio results and used to analyze the proton dynamics in the hydrogen bond and the influence of the excitation of low-frequency hydrogen-bond vibrations on the proton tunneling splittings. The energy of tunneling-split vibrational sublevels of the high-frequency tunneling mode have been calculated for its ground and first excited vibrational state for the series of excitations of the coupled low-frequency intramolecular hydrogen-bond modes. The promoting and suppressing effect of the low-frequency modes on the proton splittings was shown in the ground and first excited vibrational state of the tunneling mode. The vibrational sublevels form the two separate semicontinuous bands between which the absorption transitions may occur. This mechanism explains the experimentally observed splitting and doublet-component broadening of the high-frequency N-H stretching infrared (IR) absorption band.

Comparison of the Hydrogen Bond Interaction Dynamics in the Guanine and Cytosine Crystals: Ab Initio Molecular Dynamics and Spectroscopic Study.

In this work, we present the comparison study of guanine and cytosine crystals based on the hydrogen bond (HB) dynamics. The ab initio molecular dynamics gave us a base for detailed analysis. The analysis of the trajectories by power spectrum generation, as well as the fluctuation of the interaction energies, showed large differences between HB networks in the considered crystals. The charge flow is present in the guanine molecule which forms the flat surfaces in the crystals. In the cytosine zigzag structure, the charge flow is blocked. The interaction energy is significantly less stabilizing in the cytosine structure than in the guanine. Finally, the possible influence of charge transfer on the melting temperature has been discussed.

Rydberg transitions as a probe for structural changes and phase transition at polymer surfaces: an ATR-FUV-DUV and quantum chemical study of poly(3-hydroxybutyrate) and its nanocomposite with graphene.

We investigated the surface (<50 nm) of poly(3-hydroxybutyrate) (PHB) and its nanocomposite with graphene by attenuated total reflection far- and deep-ultraviolet (ATR-FUV-DUV; 145-300 nm; 8.55-4.13 eV) spectroscopy and quantum mechanical calculations. The major absorption of polymers occurs in FUV and is related to Rydberg transitions. ATR-FUV-DUV spectroscopy allows for direct measurements of these transitions in the solid phase. Using ATR-FUV-DUV spectroscopy, periodic density functional theory (DFT) and time-dependent DFT (TD-DFT), we explained the origins of the FUV-DUV absorption of PHB and provided insights into structural changes of PHB which occur upon formation of a graphene nanocomposite and upon heating of the pure polymer. The structural changes cause specific and gradual spectral variations in FUV-DUV. We systematically studied the relaxation of the polymer helix and concluded that the common feature of all models of the unfolded helix lies in a specific and consistent FUV-DUV spectral signature. Relaxed structures feature a blue-shift of the major FUV transition (non-bonding molecular orbital to Rydberg 3p and π to π*) as compared with crystalline PHB. The FUV absorption of the relaxed structures was determined to be significantly stronger than that of the crystalline state. These results are consistent with the observed temperature-dependent spectra of the pure PHB. The simulation of the thermal expansion of the crystalline polymer by a periodic-DFT study allows us to exclude the possibility that spectral variations observed experimentally are influenced by changes in the crystalline phase. We concluded that the crystallinity of PHB at the sample surface increases with an increase in graphene content in the nanocomposite. However, it is unlikely that the polymer structure inside the crystal is affected; instead the FUV-DUV spectral variations result from changes in the polymer morphology that occur at the sample surface. The phase transition of PHB is affected by temperature and addition of graphene content. These changes are likely to be the opposite of those occurring in the bulk sample.

Equivalence between the Classical and Quantum IR Spectral Density Approaches of Weak H-Bonds in the Absence of Damping.

The aim of this paper is to overhaul the quantum elucidation of the spectral density (SD) of weak H-bonds treated without taking into account any of the damping mechanisms. The reconsideration of the SD is performed within the framework the linear response theory. Working in the setting of the strong anharmonic coupling theory and the adiabatic approximation, the simplified expression of the classical SD, in the absence of dampings, is equated to be ICl(ω) = Re[∫0∞GCl(t)e-iΩt dt] in which the classical-like autocorrelation function (ACF), GCl(t), is given by GCl(t) = tr{ρ(ß){µ(0)}{µ(t)}†}. With this consideration, we have shown that the classical SD is equivalent to the line shape obtained by F(ω) = ΩICl(ω), which in turn is equivalent to the quantum SD given by IQu(ω) = Re[∫0∞GQu(t)e-iΩt dt], where GQu(t) is the corresponding quantum ACF having for expression GQu(t) = (1/ß) tr{ρ∫0ß[µ(0)}{µ(t + iλℏ)}†â€¯dλ}. Thus, we have shown that for weak H-bonds dealt without dampings, the SDs obtained by the quantum approaches are equivalent to the SDs geted by the classical approach in which the incepation ACF is, however, of quantum nature and where the line shape is the Fourier transform of the ACF times the angular frequency. It is further shown that the classical approach dealing with the SD of weak H-bonds leads identically to the result found by Maréchal and Witkowski in their pioneering quantum treatment where they ignored the linear response theory and dampings.

Electrical anharmonicity in hydrogen bonded systems: complete interpretation of the IR spectra of the Cl-H[combining right harpoon above] stretching band in the gaseous (CH3)2OHCl complex.

Following the previous developments to simulate the fully infrared spectra of weak hydrogen bond systems within the linear response theory, an extension of the adiabatic model is presented here. A general formulation including the electrical anharmonicities in the calculation of the damped autocorrelation function of weak H-bonds is adopted to facilitate the support of the additional properties, and thus the IR spectra of the Cl-H[combining right harpoon above] stretching band in the gaseous (CH3)2OHCl complex. We have explored the origins of the broadening of the Cl-H[combining right harpoon above] stretching band. We found that the main features of the lineshape are attributed to electrical anharmonicity as a consequence of the large mixed second derivatives of the dipole moment with respect to the Cl-H[combining right harpoon above] bond and of the intermonomer elongations . In addition to providing more accurate theoretical band shapes, inclusion of the electrical anharmonicity in the present model paves the way for a more complete interpretation by generating three new Franck-Condon superposed distributions.

Correlations between Structure and Near-Infrared Spectra of Saturated and Unsaturated Carboxylic Acids. Insight from Anharmonic Density Functional Theory Calculations.

By near-infrared (NIR) spectroscopy and anharmonic density functional theory (DFT) calculations, we investigate five kinds of saturated and unsaturated carboxylic acids belonging to the group of short-chain fatty acids: propionic acid, butyric acid, acrylic acid, crotonic acid, and vinylacetic acid. The experimental NIR spectra of these five kinds of carboxylic acids are reproduced by quantum chemical calculations in a broad spectral region of 7500-4000 cm-1 and for a wide range of concentrations. By employing anharmonic GVPT2 calculations on DFT level, a detailed interpretation of experimental spectra is achieved, elucidating structure-spectra correlations of these molecules in the NIR region. We emphasize the spectral features due to saturated and unsaturated alkyl chains, the location of a C═C bond within the alkyl chain, and the dimerization of carboxylic acids. In particular, the existence of a terminal C═C bond leads to the appearance of highly specific NIR bands. These pronounced bands are located at wavenumbers where no overlapping with other structure-specific bands occurs, thus making them good structural markers. Most of the spectral differences between these two groups of molecules remain subtle, and would be difficult to reliably ascribe without quantum chemically calculated NIR spectra. Moreover, anharmonic DFT calculations provide insights on the manifestation of hydrogen bonding through distinctive spectral features corresponding to cyclic dimers. The resulting spectral baseline elevation is common for all five investigated carboxylic acids, and remains consistent with previous results on acetic acid.

A spectroscopic and theoretical study in the near-infrared region of low concentration aliphatic alcohols.

The near-infrared (NIR) spectra of low-concentration (5 × 10(-3) M) solutions in CCl4 of basic aliphatic alcohols, methanol, ethanol, and 1-propanol were, for the first time, calculated by second-order vibrational perturbation theory computations and were compared with the corresponding experimental data. Density functional theory (DFT) using single hybrid (B3LYP) and double hybrid (B2PLYP) density functionals and their derivatives with additional empirical dispersion correction (B3LYP-D3 and B2PLYP-D, respectively) and second order Møller-Plesset perturbation theory were used in combination with selected basis sets including fairly new basis sets from the "spectroscopic" SNS family, double-ζ SNSD and triple-ζ SNST basis sets. Each time, anharmonic vibrational modes and intensities were calculated by using second-order vibrational perturbation theory. The effect of solvent cavity on the calculated results was included by the application of a self-consistent reaction field with a polarized continuum model. Ethanol and 1-propanol have conformational isomerism; following a conformational analysis, theoretical spectra of all isomers were calculated and their final predicted NIR spectra were obtained as Boltzmann-averaged spectra of resolved conformers. For ethanol and 1-propanol, the observed broadening of the overtone band of the OH stretching mode was well reflected by the differences in the position of the relevant band among conformational isomers of these alcohols; the effect of solvent on broadening was also discussed. Detailed band assignments in the experimental NIR spectra of the studied alcohols were proposed based on the calculation of potential energy distributions. The final accuracy of the predicted NIR spectra for each of the theoretical methods was estimated based on the errors in calculated frequencies of overtones and combination bands.

Spectroscopic and Computational Study of Acetic Acid and Its Cyclic Dimer in the Near-Infrared Region.

Anharmonic vibrational analysis of near-infrared (NIR) spectra of acetic acid was carried out by anharmonic quantum chemical calculation in a wide concentration range of its CCl4 solution. By predicting vibrational spectra of acetic acid for the first time over a wide NIR region, it was possible to elucidate the influence of the formation of acetic acid cyclic dimer on its NIR spectrum. Quantum chemical simulations were based on coupled cluster and density functional theory quantum methods. Additionally, Møller-Plesset perturbation theory was employed for the additional calculation of hydrogen bonding stabilization energies. An anharmonic vibrational analysis was performed with the use of generalized second-order vibrational perturbation theory (GVPT2). A hybrid approach was assumed, in which monomeric species was treated by CCSD(T)/aug-cc-pVDZ (harmonic approximation) and B3LYP/SNSD (anharmonic approximation) methods. For the cyclic dimer, B3LYP and B2PLYP single and double hybrid functionals, paired with an SNSD basis set, were employed. DFT calculations were augmented with additional empirical dispersion correction. It was found that quantum chemically calculated vibrational modes in the NIR region are in a good agreement with experimental data. The results of anharmonic vibrational analysis were supported by a harmonic shift analysis, for elucidating the very strong anharmonic coupling observed between stretching modes of hydrogen bonded bridge in the cyclic dimer. However, the calculated wavenumbers for combination modes of double hydrogen bonded bridge in the cyclic dimer, which are very sensitive to the formation of hydrogen bonding, were found to be underestimated by quantum chemical methods. Therefore, by band fitting, the wavenumbers and shape parameters for these bands were found, and the modeled spectra were adjusted accordingly. A high accuracy of simulated spectra was achieved, and a detailed analysis of the experimental NIR spectra of acetic acid was possible, with successful identification of numerous experimental bands, including those which originate from concentration effects. It was also found that the main spectral features observed in the NIR spectra of carboxylic acid upon the formation of hydrogen bond should be accounted for combination modes of the stretching and bending vibrations of double hydrogen-bonded bridge in the cyclic dimers of acetic acid.

Quantum-mechanical study of energies, structures, and vibrational spectra of the H(D)Cl complexed with dimethyl ether.

Interaction energies, molecular structure and vibrational frequencies of the binary complex formed between H(D)Cl and dimethyl ether have been obtained using quantum-chemical methods. Equilibrium and vibrationally averaged structures, harmonic and anharmonic wavenumbers of the complex and its deuterated isotopomer were calculated using harmonic and anharmonic second-order perturbation theory procedures with Density Functional Theory B3LYP and B2PLYP-D and ab initio Møller-Plesset second-order methods, and a 6-311++G(3d,3p) basis set. A phenomenological model describing anharmonic-type vibrational couplings within hydrogen bonds was developed to explain the unique broadening and fine structure, as well as the isotope effect of the Cl-H and Cl-D stretching IR absorption bands in the gaseous complexes with dimethyl ether, as an effect of hydrogen bond formation. Simulations of the rovibrational structure of the Cl-H and Cl-D stretching bands were performed and the results were compared with experimental spectra.

Solvent dependence of absorption intensities and wavenumbers of the fundamental and first overtone of NH stretching vibration of pyrrole studied by near-infrared/infrared spectroscopy and DFT calculations.

Near-infrared (NIR) and IR spectra were measured for pyrrole in CCl(4), CHCl(3), and CH(2)Cl(2) to study solvent dependence of absorption intensities and wavenumbers of the fundamental and first overtone of NH stretching vibration. It was found that the wavenumbers of the NH fundamental and its first overtone decrease in the order of CCl(4), CHCl(3), and CH(2)Cl(2), which is the increasing order for of the dielectric constant of the solvents. Their absorption intensities increase in the same order, and the intensity increase is more significant for the fundamental than the overtone. These results for the solvent dependence of the wavenumbers and absorption intensities of NH stretching bands of pyrrole are quite different from those due to the formation of hydrogen bonds. Quantum chemical calculations of the wavenumbers and absorption intensities of NH stretching bands by using the 1D Schrödinger equation based on the self-consistent reaction field (SCRF)/isodensity surface polarized continuum model (IPCM) suggest that the decreases in the wavenumbers of both the fundamental and the overtone of the NH stretching mode with the increase in the dielectric constant of the solvents arise from the anharmonicity of vibrational potential and their intensity increases come from the gradual increase in the slope of the dipole moment function.

Hydrogen bonding effects on the wavenumbers and absorption intensities of the OH fundamental and the first, second, and third overtones of phenol and 2,6-dihalogenated phenols studied by visible/near-infrared/infrared spectroscopy.

Visible, near-infrared (NIR) and IR spectra in the 15600-2500 cm(-1) region were measured for phenol and 2,6-difluorophenol, 2,6-dichlorophenol, and 2,6-dibromophenol in n-hexane, CCl(4), CHCl(3) and CH(2)Cl(2) to study hydrogen bonding effects and solvent dependences of wavenumbers and absorption intensities of the fundamental and the first, second, and third overtones of OH stretching vibrations. A band shift of the OH stretching vibrations from a gas state to a solution state (solvent shift) was plotted versus vibrational quantum number (v = 0, 1, 2 and 3), and it was found that there is a linear relation between the solvent shift and the vibrational quantum number. The slope of solvent shift decreases in the order of phenol, 2,6-difluorophenol and 2,6-dichlorophenol. For all of the solute molecules, the slope becomes larger with the increase in the dielectric constant of the solvents. The relative intensities of the OH stretching vibrations of phenol in CCl(4), CHCl(3), and CH(2)Cl(2) against the intensity of the corresponding OH vibration in n-hexane increase in the fundamental and the second overtone but decrease in the first and third overtones; the relative intensities show so-called "parity". The parity is more prominent for phenol that has an intermolecular hydrogen bonding than for 2,6-dihalogenated phenols that have an intramolecular hydrogen bond. These observations suggest that the intermolecular hydrogen bond between the OH group and the Cl atom plays a key role for the parity and that the intermolecular interaction between the solutes and the solvents (solvent effects) does not have a significant role in the parity.

A comparison of the hydrogen bond interaction dynamics in the adenine and thymine crystals: BOMD and spectroscopic study.

In this work we present the comparison study of Adenine and Thymine crystals based on the hydrogen bond dynamics. The ab initio molecular dynamics have been used as the base for the further studied interactions observed inside crystals. The generated power spectra, as well as the fluctuation of the interaction energies, showed large differences between hydrogen bond networks in the considered crystals. The analysis of intermolecular interactions have been done base on the reactivity descriptors as well frontiers orbitals along trajectories. The main results showed that in adenine crystals the intermolecular interactions have three directions and fluctuate, while in the thymine crystal have only two directions and are weak but stable. These results explain also on the difference between adenine and thymine melting temperature.

Theoretical study of proton tunneling in the excited state of tropolone.

Ab initio CIS/6-311++G(d,p) calculations of geometry and vibrational frequencies have been carried out in the A state of tropolone. The grids of potential energy surfaces along the coordinates of high frequency tunneling vibration and the low-frequency coupled vibration have been calculated. Two-dimensional model potentials, formed from symmetric mode coupling potential and squeezed double well potential, have been fitted to the calculated potential energy surfaces and used to analyze proton dynamics. The tunneling splittings for different vibrationally excited states have been calculated and compared with the available experimental data. The model potential energy surfaces, based on the CIS/6-311++G(d,p) calculations, give good estimation of the tunneling energy splittings in the vibrationally ground and excited states of tropolone and explain monotonic decrease in tunneling splittings with the excitation of low-frequency out-of-plane modes and increase in the tunneling splittings with the excitation of low-frequency planar modes.

Towards accurate infrared spectral density of weak H-bonds in absence of relaxation mechanisms.

Following the previous theoretical developments to completely reproduce the IR spectra of weak hydrogen bond complexes within the framework of the linear response theory (LRT), the quantum theory of the high stretching mode spectral density (SD) of weak H-bonds is reconsidered. Within the LRT theory, the SD is the one sided Fourier transform of the autocorrelation function (ACF) of the high stretching mode dipole moment operator. In order to provide more accurate theoretical bandshapes, we have explored the equivalence between the SDs given in previous studies with respect to a new quantum one, and revealed that in place of the basic equations used in the precedent works for which the SD IOld(ω)=2Re∫0∞GOld(t)e-iωtdt where the ACF GOld(t) = ⟨µ(0)µ(t)+⟩ = tr {ρ {µ(0)} {µ(t)}+}, one can use a new expression for the SD, given by INew(ω)=2ωRe∫0∞GNew(t)e-iωtdt where GNew(t)=µ(0)µ(t)+=1ßtrρB∫0ßµ(0)µ(t+iλℏ)+dλ. Here ρB is the Boltzmann density operator, µ(0) the dipole moment operator at initial time and µ(t) the dipole moment operator at time t in the Heisenberg picture, ℏ is the Planck constant, ß is the inverse of the Boltzmann factor kBT where T is the absolute temperature and kB the Boltzmann constant. Using this formalism, we demonstrated that the new quantum approach gives the same final SD as used by previous models, and reduces to the Franck-Condon progression appearing in the Maréchal and Witkowski's pioneering approach when the relaxation mechanisms are ignored. Results of this approach shed light on the equivalence between the quantum and classical IR SD approaches for weak H-bonds in absence of medium surroundings effect, which has been a subject of debate for decades.

IR Spectra of Crystalline Nucleobases: Combination of Periodic Harmonic Calculations with Anharmonic Corrections Based on Finite Models.

This work reports a theoretical study of infrared (IR) spectra of four nucleobases (adenine, cytosine, guanine, and thymine) in the crystalline state. The effects responsible for the fine spectral features were revealed, and the nonfundamental bands significantly contributing to the IR fingerprint region were successfully reproduced. Additionally, we compared the fundamental bands simulated for periodic models in harmonic approximation with the results obtained for finite models in anharmonic approximation. On this basis, we concluded that accurate description of the chemical neighborhood is more essential for the IR fingerprint region than the anharmonicity. Comparison with previous results indicates that the vibrational properties and the nature of intermolecular interactions of nucleobases in the crystalline state remain similar to those in solution. Therefore, the conclusions obtained for well-defined crystalline structures of nucleobases are general and helpful in understanding the vibrational spectra and properties of nucleobases and their derivatives. Finally, this work evidences that anharmonic force field based on finite models may be applied as an inexpensive correction to the harmonic spectrum of an infinite periodic system.

Spectroscopic study of uracil, 1-methyluracil and 1-methyl-4-thiouracil: Hydrogen bond interactions in crystals and ab-initio molecular dynamics.

Hydrogen bond networks in uracil, 1-methyluracil and 1-methyl-4-thiouracil were studied by ab initio molecular dynamics as well as analysis of the orbital interactions. The power spectra calculated by ab initio molecular dynamics for atoms involved in hydrogen bonds were analyzed. We calculated spectra by using anharmonic approximation based on the autocorrelation function of the atom positions obtained from the Born-Oppenheimer simulations. Our results show the differences between hydrogen bond networks in uracil and its methylated derivatives. The studied methylated derivatives, 1-methyluracil as well as 1-methyl-4-thiouracil, form dimeric structures in the crystal phase, while uracil does not form that kind of structures. The presence of sulfur atom instead oxygen atom reflects weakness of the hydrogen bonds that build dimers.

Spectra-structure correlations of saturated and unsaturated medium-chain fatty acids. Near-infrared and anharmonic DFT study of hexanoic acid and sorbic acid.

Quantum chemical reproduction of entire NIR spectra is a new trend, enabled by contemporary advances in the anharmonic approaches. At the same time, recent increase of the importance of NIR spectroscopy of biological samples raises high demand for gaining deeper understanding of NIR spectra of biomolecules, i.e. fatty acids. In this work we investigate saturated and unsaturated medium-chain fatty acids, hexanoic acid and sorbic acid, in the near-infrared region. By employing fully anharmonic density functional theory (DFT) calculations we reproduce the experimental NIR spectra of these systems, including the highly specific spectral features corresponding to the dimerization of fatty acids. Broad range of concentration levels from 5·10-4M in CCl4 to pure samples are investigated. The major role of cyclic dimers can be evidenced for the vast majority of these samples. A highly specific NIR feature of fatty acids, the elevation of spectral baseline around 6500-4000cm-1, is being explained by the contributions of combination bands resulting from the vibrations of hydrogen-bonded OH groups in the cyclic dimers. Based on the high agreement between the calculated and experimental NIR spectra, a detailed NIR band assignments are proposed for hexanoic acid and sorbic acid. Subsequently, the correlations between the structure and NIR spectra are elucidated, emphasizing the regions in which clear and universal traces of specific bands corresponding to saturated and unsaturated alkyl chains can be established, thus demonstrating the wavenumber regions highly valuable for structural identifications.

Infrared Spectroscopy and Born-Oppenheimer Molecular Dynamics Simulation Study on Deuterium Substitution in the Crystalline Benzoic Acid.

In this study we present complementary computational and experimental studies of hydrogen bond interaction in crystalline benzoic acid and its deuterated and partially deuterated derivatives. The experimental part of the presented work includes preparation of partially deuterated samples and measurement of attenuated total reflection (ATR)-FTIR spectra. Analysis of the geometrical parameters and time course of dipole moment of crystalline benzoic acid and its deuterated and partially deuterated derivatives by Born-Oppenheimer molecular dynamics (BOMD) enabled us to deeply analyze the IR spectra. Presented simulations based on BOMD gave us opportunity to investigate individual motion and its contribution to the IR spectra. The band contours calculated using Fourier transform of autocorrelation function are in quantitative agreement with the experimental spectra. Characterization of single bands was carried out by "normal coordinate analysis". The salient point of our study is a comparison of the spectra of the deuterated and partially deuterated crystalline benzoic acid with that of the nondeuterated one. Furthermore, we have applied the principal component analysis for analysis of the number of components in partially deuterated systems. In this study, we reveal that the arrangements of hydrogen and deuterium atoms in partially deuterated samples are random.

Theoretical modeling of infrared spectra of hydrogen-bonded crystals of salicylic acid.

A theoretical model for the infrared spectra in the O-H stretching region of hydrogen-bonded salicylic acid is presented. Based on the model, infrared spectrum in the O-H stretching region is calculated for salicylic acid and compared with the experimental one. The experimental and theoretical spectra are in good agreement.