Ab initio and DFT studies of the vibrational spectra of hydrogen-bonded PhOH...(H2O)4 complexes

The vibrational characteristics (vibrational frequencies and infrared intensities) for the hydrogen-bonded complex of phenol with four water molecules PhOH...(H2O)4 (structure 4A) have been predicted using ab initio and DFT (B3LYP) calculations with 6-31G(d,p) basis set. The changes in the vibrational characteristics from free monomers to a complex have been calculated. The ab initio and B3LYP calculations show that the observed four intense bands at 3299, 3341, 3386 and 3430 cm(-1) can be assigned to the hydrogen-bonded OH stretching vibrations in the complex PhOH...(H2O)4 (4A). The complexation leads to very large red shifts of these vibrations and very strong increase in their IR intensity. The predicted red shifts for these vibrations with B3LYP/6-31G(d,p) calculations are in very good agreement with the experimentally observed. It was established that the phenolic OH stretching vibration is the most sensitive to the hydrogen bonding. The predicted red-shift with the B3LYP/6-31G(d,p) calculations for the most stable ring structure 4A (-590 cm(-1)) is in better agreement with the experimentally observed than the red-shift, predicted with SCF/6-31G(d,p) calculations. The magnitude of the wavenumber shift is indicative of relatively strong OH...H hydrogen-bonded interaction. The complexation between phenol and four water molecules leads to strong increase of the IR intensity of the phenolic OH stretching vibration (up to 38 times).     

Theoretical study of the vibrational spectra of the hydrogen-bonded systems between pyridine-3-carboxamide (nicotinamide) and DMSO

The vibrational characteristics (vibrational frequencies and infrared intensities) for the hydrogen-bonded systems of nicotinamide (NA(Z) and NA(E)) with dimethyl sulfoxide (DMSO) have been predicted using ab initio SCF/6-31G(d,p) and DFT (BLYP/6-311++G(d,p)) calculations. The changes in the vibrational characteristics from free monomers to a complex have been calculated. The ab initio and BLYP calculations show that the complexation between nicotinamide (NA(Z) and NA(E)) and DMSO leads to large red shifts of the stretching vibrations for the hydrogen-bonded N-H bonds of nicotinamide and very strong increase in their IR intensity. The results from the BLYP/6-311++G(d,p) calculations show that the predicted red shifts of the nu(s)(NH) and nu(as)(NH) vibrations for the complex NA(E)-DMSO (1:2) (Deltanu(as)(NH)=-186 cm(-1) and Deltanu(s)(NH)=-198 cm(-1)) are in better agreement with the experimentally measured. The magnitudes of the wavenumber shifts are indicative of strong NH...O hydrogen-bonded interactions in both complexes. The calculations predict an increase of the IR intensity of nu(s)(NH) and nu(as)(NH) vibrations in the complexes up to 14 times. Having in mind that in more cases the predicted changes in the vibrational characteristics for the complexes studied are very near, it could be concluded that both conformers of nicotinamide, Z-conformer and E-conformer, are present in the solution forming the hydrogen-bonded complexes with DMSO.     

Theoretical study of the structures and vibrational spectra of the hydrogen-bonded systems of 4-cyanophenol with N-bases

The structural and vibrational features of the hydrogen bonded complexes of 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) with one and two 4-CNPhOH molecules have been studied extensively by ab initio SCF/6-31G(d,p) and BLYP calculations with various basis sets: 6-31G(d,p), 6-31+G(d,p) and 6-31++G(d,p). Full geometry optimization was made for the complexes studied. The nature of the hydrogen bonding and the influence of the hydrogen bonding on the structural and vibrational characteristics of the monomers have been investigated. The corrected values of the dissociation energy for the hydrogen-bonded complexes have been calculated in order to estimate their stability. The calculated values of the dissociation energy per phenol molecule indicate that the complex: TBD: 4-CNPhOH (1:1) is more stable than the complex: TBD: 4-CNPhOH (1:2). The changes in the structural and vibrational characteristics upon hydrogen bonding depend on the strength of the hydrogen bonds. In agreement with the experiment, the calculations show that the complexation between TBD and 4-CNPhOH leads to considerably changes in the vibrational characteristics of the stretching O-H vibration. The vibrational frequency of the O-H stretching vibration is shifted to lower wave numbers upon hydrogen bonding. The predicted frequency shifts Deltanu(O-H) for the complexes--TBD: 4-CNPhOH (1:1) and TBD: 4-CNPhOH (1:2) are in the range from -190 cm(-1) to -586 cm(-1). In the same time the IR intensity of the O-H stretching vibration increases dramatically in the hydrogen-bonded complexes.     

FTIR and Ab initio investigations of the MTBE-water complex

The infrared spectrum of methyl tert-butyl ether (MTBE) in liquid water has been studied using both FTIR absorption and FTIR-ATR spectroscopy in conjunction with ab initio calculations. Compared to the liquid MTBE IR spectrum, the C-O and C-C stretching vibrational frequencies of MTBE in water are found to shift to the red and blue by up to 26 and 9 cm (-1), respectively. Ab initio calculations suggest that these shifts are caused by complexation of the MTBE molecule with water molecules through hydrogen bonding. Our observation of the vibrational frequency shifts in the IR spectrum of MTBE in water provides the IR spectroscopic evidence of organics-water complexes in the diluted aqueous solution. The implication of the effect of the hydrogen bond in organics-water complexation on solvation and reactivity of the organic compound in aqueous chemical processes is discussed.     

Structure, stability and vibrational spectrum of the hydrogen-bonded complex between HNO3 and H2O. Ab initio and DFT studies

The structure, stability and vibrational spectrum of the binary complex between HONO2 and H2O have been investigated using ab initio calculations at SCF and MP2 levels with different basis sets and B3LYP/6-31G(d,p) calculations. Full geometry optimization was made for the complex studied. It was established that the hydrogen-bonded H2O...HONO2 complex has a planar structure. The corrected values of the dissociation energy at the SCF and MP2 levels and B3LYP calculations are indicative of relatively strong OH...O hydrogen-bonded interaction. The changes in the vibrational characteristics (vibrational frequencies and infrared intensities) arising from the hydrogen bonding between HONO2 and H2O have been estimated by using the ab initio calculations at SCF and MP2 levels and B3LYP/6-31G(d,p) calculations. It was established that the most sensitive to the complexation is the stretching O-H vibration from HONO2. In agreement with the experiment, its vibrational frequency in the complex is shifted to lower wavenumbers. The predicted frequency shift with the B3LYP/6-31G(d,p) calculations (-439 cm(-1)) is in the best agreement with the experimentally measured (-498 cm(-1)). The intensity of this vibration increases dramatically upon hydrogen bonding. The ab initio calculations at the SCF level predict an increase up to five times; at the MP2 level up to 10 times and the B3LYP/6-31G(d,p) predicted increase is up to 17 times. The good agreement between the predicted values of the frequency shifts and those experimentally observed show that the structure of the hydrogen-bonded complex H2O...HONO2 is reliable.     

Ab initio prediction of the vibrational spectrum of the hydrogen bonded complex O2N...HONO2

The changes in the structural parameters and vibrational characteristics (vibrational frequencies, infrared intensities and Raman activities) arising from the hydrogen bonding between NO(2) and HONO(2) have been studied employing ab initio 6-31G(d, p)/UHF and 6-31+G(d, p)/UHF, and B3LYP/6-31G(d, p) calculations. The charge rearrangement upon hydrogen bonding have been, estimated using the Mulliken population analyses. It was established that the complexation between NO(2) and HONO(2) leads to changes in the structural parameters and the vibrational characteristics of the monomers. The most sensitive to the hydrogen bond formation are the vibrational characteristics of the normal modes of the monomer bonds participating in the hydrogen bonding. The predicted shifts in the vibrational frequencies by ab initio and B3LYP/6-31G(d, p) calculations are in very good agreement with the experimentally observed, which is an evidence for the reliance of the studied structure.     

Hydrogen-bonded complexes of nitrous and nitric acids with ethene Ab initio and DFT studies

The complexes formed by ethene with nitric and nitrous (trans and cis) acids have been investigated by ab initio (SCF and MP2) and B3LYP calculations with 6-311++G(d,p) basis set. Full geometry optimisation has been performed for the complexes studied. The most stable structures of the complexes are established. Bearing in mind the corrected values of the dissociation energy the studied hydrogen-bonded complexes can be ordered as follows: C(2)H(4)...HONO(2)>C(2)H(4)...HONO-trans>C(2)H(4)...HONO-cis. In the complexes the acids act as proton donors forming the pi-type of hydrogen bond with ethene. The predicted changes in the vibrational characteristics (vibrational frequencies and infrared intensities) arising from the hydrogen bonding are in good agreement with the experimentally measured. The predicted frequency shift of the stretching OH vibration in the nitric acid is largest (-210 cm(-1)), followed by the shifts in the trans-HONO (-141 cm(-1)) and cis-HONO (-109 cm(-1)). The calculations predict an increase of the IR intensity of the stretching O-H vibration in the complexes from 6 to 10 times.     

Structure and vibrational spectrum of the hydrogen-bonded system between 4-tert-butylphenol and N-bases: Ab initio and DFT studies

The structural and vibrational characteristics of the hydrogen-bonded system between 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) and 4-tert-butylphenol have been investigated employing ab initio and DFT calculations at different basis sets. The calculations show that the optimized structure of the studied system is cyclic. The corrected values of the dissociation energy for the hydrogen-bonded complex have been calculated in order to estimate its stability. The influence of the hydrogen bonding on the properties of the monomers (TBD and 4-tert-butylphenol) has been investigated. The hydrogen bonding between TBD and 4-tert-butylphenol leads to changes in the structural (bond lengths and angles) and vibrational (vibrational frequencies and infrared intensities) characteristics of the monomers. It was established that the TBD molecule is considerably deformed upon hydrogen bonding, while the deformation of the 4-t-BuPhOH is smaller. In agreement with the experiment, the calculations show that the stretching O-H vibration from 4-tert-butylphenol is shifted to lower frequency upon hydrogen bonding. The predicted frequency shift Deltanu(O-H) (-338cm(-1)) is in very good agreement with the experimentally observed (-351cm(-1)). In the same time the IR intensity of the nu(O-H) increases dramatically in the hydrogen-bonded system.     

IR spectroscopy of hydrogen-bonded 2-fluoropyridine-methanol clusters

The electronic and infrared spectra of 2-fluoropyridine-methanol clusters were observed in a supersonic free jet. The structure of hydrogen-bonded clusters of 2-fluoropyridine with methanol was studied on the basis of the molecular orbital calculations. The IR spectra of 2-fluoropyridine-(CH3OH)n(n = 1-3) clusters were observed with a fluorescence-detected infrared depletion (FDIR) technique in the OH and CH stretching vibrational regions. The structures of the clusters are similar to those observed for 2-fluoropyridine-(H2O)n (n = 1-3) clusters. The existence of weak hydrogen bond interaction through aromatic hydrogen was observed in the IR spectra. The theoretical calculation also supports the result. The vibrational frequencies of CH bonds in CH3 group are affected by hydrogen bond formation although these bonds do not directly relate to the hydrogen bond interaction. The B3LYP/6-311 ++G(d,p) calculations reproduce well the vibrational frequency of the hydrogen-bonded OH stretching vibrations. However, the calculated frequency of CH stretching vibration could not reproduce the IR spectra because of anharmonic interaction with closely lying overtone or combination bands for nu3 and nu9 vibrations. The vibrational shift of nu2 vibration is reproduced well with molecular orbital calculations. The calculation also shows that the frequency shift of nu2 vibration is closely related to the CH bond length at the trans position against the OH bond in hydrogen-bonded methanol.     

Comparative study of the hydrogen-bonded complexes of phenol and o-cyanophenol with CO Ab initio and DFT approachs

The structures, stability and vibrational spectra of the hydrogen-bonded complexes of carbon monoxide (CO) with phenol and o-cyanophenol (syn and anti) have been studied using ab initio and DFT calculations. Full geometry optimization has been performed for the studied complexes by DFT (BLYP/6-311++G(d,p)) calculations. The calculations show that the hydrogen-bond formation of carbon monoxide (CO) with phenol and o-cyanophenol (syn and anti) leads to the following stable structures: C6H5OH...CO (1A); C6H5OH...OC (1B); (syn) o-CNC6H4OH...CO (2A-syn); (syn) o-CNC6H4OH...OC (2B-syn); (anti) o-CNC6H4 OH...CO (2A-anti) and (anti) o-CNC6H4OH...OC (2B-anti). Having in mind the corrected values of the dissociation energy, the studied hydrogen-bonded complexes can be ordered according their stability as follows: 2A-anti>2A-syn>1A>2B-anti>1B>2B-syn. The predicted red-shifts for the nuOH vibration with the B3LYP/6-311++G(d,p) calculations for the structures 1A (-46 cm-1), 2A-syn (-60 cm-1) and 2A-anti (-73 cm-1) are in very good agreement with the experimentally observed. The magnitudes of the wavenumber shifts are indicative of relatively weak OH...C hydrogen-bonded interactions. The calculations predict an increase of the IR intensity of the nuOH vibration in the complexes 1A, 2A-anti and 2A-syn up to five times.     

Effect of hydrogen bonding and cooperativity on stretching force constants of formamide

Stretching force constants for formamide and its seven associated species involving two to four molecules hydrogen-bonded through linear and cyclic configurations and 10 structures containing formamide hydrogen-bonded with one to five water molecules are reported. Since ab initio calculations are rather inconvenient to perform on such big clusters and are time-consuming, CNINDO MO calculations were carried out using the gradient method. The results demonstrate, on the one hand, the feasibility of semiempirical calculations for the evaluation of trends in force constants for big clusters where generally ab initio calculations become much involved and, on the other hand, explain the effect of hydrogen bonding and cooperativity on force constants and vibrational spectra of biologically important systems composed of formamide in the condensed phase and its aqueous solutions. The C?O and N? H stretching force constants are found to reduce significantly on hydrogen bonding. The reduction in force constant is further enhanced when two cyclic dimers become associated through a linear hydrogen bond. The results indicate justification for the stabilization of the formamide structure with two cyclic dimers hydrogen-bonded together. The reduction in the force constants on hydrogen bonding also reflect the cooperativity contribution. The C?O and C? N stretching force constants for the structures corresponding to formamide in liquid and aqueous solution phases are in agreement with the experimental vibrational frequencies reported.     

Vibrations and hydrogen bonding in porphycene

Combined use of IR, Raman, neutron scattering and fluorescence measurements for porphycene isolated in helium nanodroplets, supersonic jet and cryogenic matrices, as well as for solid and liquid solutions, resulted in the assignments of almost all of 108 fundamental vibrations. The puzzling feature of porphycene is the apparent lack of the N-H stretching band in the IR spectrum, predicted to be the strongest of all bands by standard harmonic calculations. Theoretical modeling of the IR spectra, based on ab initio molecular dynamics simulations, reveals that the N-H stretching mode should appear as an extremely broad band in the 2250-3000 cm(-1) region. Coupling of the N-H stretching vibration to other modes is discussed in the context of multidimensional character of intramolecular double hydrogen transfer in porphycene. The analysis can be generalized to other strongly hydrogen-bonded systems.     

Ab initio study of the vibrational spectra of the hydrogen-bonded nitric acid dimer.

The changes in the vibrational characteristics characterizing the dimerization of nitric acid have been investigated by ab initio calculations at the MP2 level, with 6-31G(d,p) and 6-31 + G(d,p) basis sets, and B3LYP/6-31G(d,p) calculations. The most consistent agreement between the computed values of the frequency shifts for the planar fully symmetric structure (2A) and those experimentally observed suggests that this structure is preferred. It was established that the most sensitive to the complexation is the stretching O-H vibration. The values of the frequency shift (-306 cm(-1)) is indicative for the formation of the relatively strong hydrogen bonds. The calculations predict an increase of the infrared intensity of the stretching O-H vibration in the nitric acid dimer more than 26 times.     

Using Raman Spectroscopy and ab initio Calculations to Investigate Intermolecular Hydrogen Bonds in Binary Mixture (Tetrahydrofuran+Water)

We analyzed the properties and structures of the hydrogen-bonded complexes of tetrahydrofuran(THF) and water by means of experimental Raman spectra and ab initio calculations.The optimized geometries and vibrational frequencies of the neat THF molecule and its hydrogen-bonded complexes with water(THF/H2O) were calculated at the MP2/6-311+G(d,p) level of theory.We found that the intermolecular hydrogen bonds which are formed from the binary mixtures of the neat THF and water with different molar ratios could...     

Ab initio prediction of the vibrational spectra of the hydrogen‐bonded complexes between CO and HONO2

The vibrational characteristics (vibrational frequencies and infrared intensities) for free and complexed CO and HONO₂ have been predicted using ab initio calculations at SCF and MP2 levels with different basis sets and B3LYP/6?31G(d,p) calculations. The ab initio calculations show that the complexation between HONO₂ and CO leads to two stable structures: CO … HONO₂ (1A) and OC … HONO₂ (1B). The changes in the vibrational characteristics from free monomers to complexes have been estimated. It was established that the most sensitive to the complexation is the stretching O? H vibration. In agreement with the experiment, its vibrational frequency in the complexes is shifted to lower frequency (Δν = ?123 cm^?1). The magnitude of the wave number shift is indicative of relatively strong hydrogen‐bonded interaction. The ab initio calculations at different levels predict an increase of the infrared intensity of the stretching O? H vibration for structure 1A more than five times and for structure 1B more than nine times. The most consistent agreement between the computed values of the frequency shifts for structure 1B and those experimentally observed suggests that this structure is preferred. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003     

Theoretical study of the structures, stability and vibrational spectra of the nitrous acid complexes with CH4

The structures, stability and vibrational spectra of the binary complexes CH4...HONO-trans and CH4...HONO-cis have been investigated using ab initio calculations at the SCF and MP2 levels with 6-311++G(d,p) basis set and B3LYP calculations with 6-31G(d,p) and 6-31+G(d,p) basis sets. Full geometry optimization was made for the complexes studied. It was established that the complex CH4...HONO-trans is more stable by 0.41 kcal mol(-1) than the complex CH4...HONO-cis. The accuracy of the ab initio calculations have been estimated by comparison between the predicted values of the vibrational characteristics (vibrational frequencies and infrared intensities) and the available experimental data. It was established, that the methods, used in this study are well adapted to the problem under examination. The predicted values with the B3LYP calculations are very near to the results, obtained with 6-311++G(d,p)/MP2. The changes in the vibrational characteristics of methane and trans-, cis-nitrous acid upon formation of the hydrogen bond show that the complexes CH4...HONO-trans and CH4...HONO-cis have geometry in which the OH group interacts with a methane molecule forming a single hydrogen bond. This fact is confirmed by relatively strong perturbation of the OH stretching vibration to lower frequencies and an increase of the infrared intensity of this vibration up to three times upon hydrogen bonding.     

Infrared spectroscopy of hydrogen-bonded 2-fluoropyridine-water clusters in supersonic jets

The hydrogen-bonded clusters of 2-fluoropyridine with water were studied experimentally in a supersonic free jet and analyzed with molecular orbital calculations. The IR spectra of 2-fluoropyridine-(H2O)(n) (n = 1 to 3) clusters were observed with a fluorescence detected infrared depletion (FDIR) technique in the OH and CH stretching vibrational regions. The frequencies of OH stretching vibrations show that water molecules bond to the nitrogen atom of 2-fluoropyridine in the clusters. The hydrogen-bond formation between aromatic CH and O was evidenced in the 1:2 and 1:3 clusters from the experimental and calculated results. The overtone vibrations of the OH bending mode in hydrogen-bonded water molecules appear in the IR spectra, and these frequencies become higher with the increase of the number of water molecules in the clusters. The band structure of the IR spectra in the CH stretching region changes depending on the number of coordinating water molecules.     

Matrix isolation infrared and ab initio study of the hydrogen bonding between formic acid and water

The infrared spectra of the formic acid-water complexes isolated in argon matrices are reported. Both supersonic jet expansion and a conventional effusive source followed by trapping in solid argon at 10K are used to obtain the matrices. The experimental IR spectra are compared to the data obtained from high level ab initio (MP2) and DFT (B3LYP) calculations with 6-311++G(d,p) and aug-cc-pVTZ basis sets. The complex formation results in red shifts in the C=O and O-H stretching vibrations and a blue shift in the C-O stretching vibration of formic acid. The O-H stretching modes of water also exhibit pronounced red shifts. Both the MP2 and B3LYP calculations located three minima corresponding to cyclic HCOOH...H2O complexes with two hydrogen bond interactions. The binding energies are -10.3, -5.1, and -3.5 kcal mol(-1), respectively, for the three complexes at the MP2/ aug-cc-pVTZ level, corrected for the basis set superposition error (BSSE) using the Boys-Bernardi counterpoise scheme. Comparison of the calculated frequencies of the three complexes with the matrix IR spectrum reveals that the lowest energy complex is formed. In addition, a complex of formic acid with two water molecules is observed.     

Vibrational frequencies and infrared intensities of the hydrogen-bonded complexes of nitrous acid with ethers: ab initio and DFT studies

The vibrational spectra of the binary complexes formed by HONO-trans and HONO-cis with dimethyl and diethyl ethers have been investigated using ab initio calculations at the SCF and MP2 levels with 6-311++G(d,p) basis set and B3LYP calculations with 6-31G(d,p) and 6-31+G(d,p) basis sets. Full geometry optimisation was made for the complexes studied. The accuracy of the ab initio calculations have been estimated by comparison between the predicted values of the vibrational characteristics (vibrational frequencies and infrared intensities) and the available experimental data. It was established, that the methods, used in this study are well adapted to the problem under examination. The predicted values with the B3LYP calculations are very near to the results, obtained with 6-311++G(d,p)/MP2. The ab initio and DFT calculations show that the changes in the vibrational characteristics (vibrational frequencies and infrared intensities) upon hydrogen bonding for the hydrogen-bonded complex (CH3)2O...HONO-trans are larger than for the complex (CH3)2O...HONO-cis.     

NIR-FT Raman and infrared spectra and ab initio computations of glycinium oxalate

The single crystals of glycinium oxalate are grown by slow evaporation technique and vibrational spectral analysis is carried out using NIR-FT Raman and FT-IR spectra. The ab initio quantum computations are also performed at HF/6-31 G(d) level to derive the optimized geometry, atomic charges and vibrational frequencies of the glycinium oxalate molecule. Vibrational analysis indicates the presence of peculiar intermolecular C-H...O hydrogen bonding interaction producing "blue shift" of C-H stretching frequency. The vibrational spectra confirm the existence of NH3(+) in glycinium oxalate. Hydroxyl vibrations with different inter and intra molecular H-bonding are analysed, supported by computed results.