Structure and vibrational assignment of the enol form of 1,1,1-trifluoro-2,4-pentanedione

Molecular structure of 1,1,1-trifluoro-pentane-2,4-dione, known as trifluoro-acetylacetone (TFAA), has been investigated by means of Density Functional Theory (DFT) calculations and the results were compared with those of acetylacetone (AA) and hexafluoro-acetylacetone (HFAA). The harmonic vibrational frequencies of both stable cis-enol forms were calculated at B3LYP level of theory using 6-31G** and 6-311++G** basis sets. We also calculated the anharmonic frequencies at B3LYP/6-31G** level of theory for both stable cis-enol isomers. The calculated frequencies, Raman and IR intensities, and depolarization ratios were compared with the experimental results. The energy difference between the two stable cis-enol forms, calculated at B3LYP/6-311++G**, is only 5.89 kJ/mol. The observed vibrational frequencies and Raman and IR intensities are in excellent agreement with the corresponding values calculated for the most stable conformation, 2TFAA. According to the theoretical calculations, the hydrogen bond strength for the most stable conformer is 57 kJ/mol, about 9.5kJ/mol less than that of AA and about 14.5 kJ/mol more than that of HFAA. These hydrogen bond strengths are consistent with the frequency shifts for OH/OD stretching and OH/OD out-of-plane bending modes upon substitution of CH(3) groups with CF(3) groups. By comparing the vibrational spectra of both theoretical and experimental data, it was concluded that 2TFAA is the dominant isomer.     

Vibrational assignment and structure of dibenzoylmethane. A density functional theoretical study

Molecular structure and vibrational frequencies of 1,3-diphenyl-1,3-propanedione, known as dibenzoylmethane (DBM), have been investigated by means of density functional theory (DFT) calculations. The results were compared with those of benzoylacetone (BA) and acetylacetone (AA), the parent molecule. IR and Raman spectra of DBM and its deuterated analogue were clearly assigned.The calculated hydrogen bond energy of DBM is 16.15 kcal/mol, calculated at B3LYP/6-311++G** level of theory, which is 0.28 kcal/mol more than that of AA. This result is in agreement with the vibrational and NMR spectroscopy results. The molecular stability and the hydrogen bond strength were investigated by applying the Natural Bond Orbital analysis (NBO) and geometry calculations. The theoretical calculations indicate that the hydrogen bond in DBM is relatively stronger than that in BA and AA.     

Ionic liquid based on α-amino acid anion and N7,N9-dimethylguaninium cation ([dMG][AA]): theoretical study on the structure and electronic properties

The interactions between five amino acid based anions ([AA](-) (AA = Gly, Phe, His, Try, and Tyr)) and N7,N9-dimethylguaninium cation ([dMG](+)) have been investigated by the hybrid density functional theory method B3LYP together with the basis set 6-311++G(d,p). The calculated interaction energy was found to decrease in magnitude with increasing side-chain length in the amino acid anion. The interaction between the [dMG](+) cation and [AA](-) anion in the most stable configurations of ion pairs is a hydrogen bonding interaction. These hydrogen bonds (H bonds) were analyzed by the quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis. Finally, several correlations between electron densities in bond critical points of hydrogen bonds and interaction energy as well as vibrational frequencies in the most stable configurations of ion pairs have been checked.     

Molecular structure and vibrational assignment of α‐chloro acetylacetone: A density functional theory study

The intramolecular hydrogen bond, molecular structure, and vibrational frequencies of α‐chloro acetylacetone have been investigated. Fourier transform infrared and Fourier transform Raman spectra of this compound and its deuterated analogue were recorded in the regions 400–4,000 cm^?1 and 50–4,000 cm^?1, respectively. Rigorous normal coordinate analysis has been performed at the B3LYP/6‐311++G** level of theory for purposes of comparison. The complete vibrational assignment for TFAA has been made on the basis of the calculated potential energy distribution. We also applied the atoms in molecules theory and natural bond orbital method for the analysis of the hydrogen bond in α‐Chloro acetylacetone and acetylacetone. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Experimental and theoretical study of the hydration of phosphate groups in esters of biological interest

We have studied the influence of different groups esterified to phosphates on the strength of the interaction of the PO bond with one water molecule. Experimental vibrational spectra of PO(4)3-, HPO4(2-), H2PO4-, phosphoenolpiruvate (PEP) and ortho-phosphocholamine (o-PC) were obtained by means of FTIR spectroscopy. Geometry calculations were performed using standard gradient techniques and the default convergence criteria as implemented in GAUSSIAN 98 Program. In order to assess the behaviour of such DFT theoretical calculations using B3LYP with 6-31G* and 6-311++G** basis sets, we carried out a comparative work for those compounds. The results were then used to predict the principal bands of the vibrational spectra and molecular parameters (geometrical parameters, stabilisation energies, electronic density). In this work, the relative stability and the nature of the PO bond in those compounds were systematically and quantitatively investigated by means of Natural Bond Order (NBO) analysis. The topological properties of electronic charge density are analysed employing Bader's Atoms in Molecules theory (AIM). The hydrogen bonding of phosphate groups with water is highly stable and the PO bond wavenumbers are shifted to lower experimental and calculated values (with the DFT/6-311++G** basis set). Accordingly, the predicted order of the relative stability of the hydrogen bonding of the water molecule to the PO bond of the investigated compounds is: PO(4)3->HPO4(2-)>H2PO4->phosphoenolpiruvate>phosphocholamine for the two basis sets used.     

Intramolecular hydrogen bond, molecular structure and vibrational assignment of tetra-acetylethane. A density functional study

The intramolecular hydrogen bond, molecular structure and vibrational frequencies of tetra-acetylethane have been investigated by means of high-level density functional theory (DFT) methods with most popular basis sets. Fourier transform infrared and Fourier transform Raman spectra of this compound and its deuterated analogue were recorded in the regions 400-4000 cm(-1) and 40-4000 cm(-1), respectively. The calculated geometrical parameters of tetra-acetylethane were compared to the experimental results of this compound and its parent molecule (acetylacetone), obtained from X-ray diffraction. The O...O distance in tetra-acetylethane, about 2.424A, suggests that the hydrogen bond in this compound is stronger than acetylacetone. This conclusion is well supported by the NMR proton chemical shifts and O-H stretching mode at 2626 cm(-1). Furthermore, the calculated hydrogen bond energy in the title compound is 17.22 kcal/mol, which is greater than the acetylacetone value. On the other hand, the results of theoretical calculations show that the bulky substitution in alpha-position of acetylacetone results in an increase of the conjugation of pi electrons in the chelate ring. Finally, we applied the atoms in molecules (AIM) theory and natural bond orbital method (NBO) for detail analyzing the hydrogen bond in tetra-acetylethane and acetylacetone. These results are in agreement with the vibrational spectra interpretation and quantum chemical calculation results. Also, the conformations of methyl groups with respect to the plane of the molecule and with respect to each other were investigated.     

Substituent effect on structure,electron density,and intramolecular hydrogen bonding in nitroso‐oxime methane

Density functional calculations with Beck's three‐parameter hybrid method using the correlation functional of Lee, Yang, and Parr (B3LYP) were carried out for investigation of the intramolecular hydrogen bond strength in Nitroso‐oxime methane and its derivatives. Also, vibrational frequencies for them were calculated at the same level of theory. The π‐electron delocalization parameter (Q) and as a geometrical indicator of a local aromaticity, the geometry‐based harmonic oscillator measure of aromaticity index has been applied. Additionally, the linear correlation coefficients between substituent constants and selected parameters in R position have calculated. The obtained results show that the hydrogen bond strength is mainly governed by the resonance variations inside the chelate ring induced by the substituent groups. The topological properties of the electron density distributions for O? H ··· O intramolecular bridges have been analyzed in terms of the Bader theory of atoms in molecules (AIM). Correlations between the H‐bond strength and topological parameters have been also studied. The electron density (ρ) and Laplacian (?²ρ) properties, estimated by AIM calculations, show that O ··· H bond have low ρ and negative (?²ρ) values (consistent with covalent character of the HBs), whereas O? H bond have positive (?²ρ) Furthermore, the analysis of hydrogen bond in this molecule and its derivatives by quantum theory of natural bond orbital (NBO) methods fairly support the ab initio results. Natural population analysis data, the electron density, and Laplacian properties as well as υ(O? H) and γ(O? H) were further used for estimation of the hydrogen bonding interactions and the forces driving their formation. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Structure and vibrational spectra of the enol form of hexafluoro-acetylacetone. A density functional theoretical study

Molecular and vibrational structure of 1,1,1,6,6,6-hexafluoropentane-2,4-dione (hexafluoro-acetylacetone) have been investigated by means of density functional theory (DFT) calculations and have been compared with those of acetylacetone, the parent molecule. According to the theoretical calculations HFAA has an asymmetric structure with hydrogen bond strength of about 12 kcal mol(-1), about 6 kcal mol(-1) less than that of acetylacetone. This weakening of hydrogen bond is consistent with frequency shifts for OH/OD stretching, OH/OD out of plane bending and O...O stretching modes upon substitution of methyl hydrogen atoms with fluorine atoms. The symmetric structure based on electron diffraction data is interpreted as superposition of two asymmetric structures.     

Modeling of hydrogen bonds in monohydrated 2,4-dithiothymine: an ab initio and AIM study

Twelve tautomers of 2,4-dithiothymine are calculated at the MP2/6-31+G(d) level, and the most stable one is referred to the di-keto form (P12). Then four H-bonded complexes between P12 and water are optimized at the MP2/6-31+G(d) level of theory. The calculation of vibrational frequencies and natural bond orbital analysis are also carried out at the same level to investigate the hydrogen bonds involved in all the systems. Within all the four complexes, three types of hydrogen bonds are formed, in which the O-H...S and N-H...O bonds are the normal bonds with the X-H bond elongation and red shift of the corresponding stretch frequencies, while the C-H...O interaction is an improper, blue-shifting hydrogen bond accompanied with the contraction of the C-H bond and a blue shift of the C-H stretch frequency. The topological properties are investigated with the atoms-in-molecules (AIM) theory. The NMR chemical shielding for the isolated and the four monohydrated 2,4-dithiothymine are calculated using the "gauge-including atomic orbital" (GIAO) method. The 1H chemical shifts are influenced by the formation of hydrogen bonds.     

Vibrational assignment, structure and intramolecular hydrogen bond study of 3-amino-1-phenyl-2-buten-1-one

Fourier transform infrared and Fourier transform Raman spectra of 3-amino-1-phenyl-2-buten-1-one and its deuterated analogue were recorded in the regions 400-4,000 and 150-4,000 cm(-1), respectively. Furthermore, the molecular structure and vibrational frequencies of title compound were investigated by a series of density functional theoretical, DFT, and ab initio calculations at the post-Hartree-Fock (MP2) level. Although, the calculated frequencies are generally in agreement with the observed spectra but the DFT results are in much better quantitative agreement with the observed spectra than the MP2 results. The observed wavenumbers were analyzed and assigned to different normal modes of vibration of the molecule. The calculated geometrical parameters show a strong intramolecular hydrogen bond with a N...O distance of 2.621-2.668 A. This bond length is shorter than that of its parent, 4-amino-3-penten-2-one (with two methyl groups in the beta-position), which is in agreement with spectroscopic results. The topological properties of the electron density contributions for intramolecular hydrogen bond in 3-amino-1-phenyl-2-buten-1-one and 4-amino-3-penten-2-one have been analyzed in term of the Bader theory of atoms in molecules (AIM). These results also support the stronger hydrogen bond in the title compound with respect to the parent molecule.     

发光共价有机骨架LCOF-NDT1荧光识别甲醛的理论研究

基于密度泛函理论(DFT)和含时密度泛函理论(TD-DFT),探究了发光共价有机骨架LCOF-NDT1与甲醛之间的分叉氢键作用.发现LCOF-NDT1与甲醛氢键作用后发光机理发生改变.氢键复合物的电子激发能减小,激发态下的氢键键长变短,氢键质子供体的~1H-NMR移向高场,氢键质子供体和受体的振动频率发生红移,均表明电子激发态下的氢键增强.氢键复合物的荧光速率系数减小,内转换速率系数增大,阐明电子激发态下氢键的增强有利于非辐射跃迁,不利于辐射跃迁,从而导致LCOF-NDT1荧光减弱或猝灭.计算结果表明LCOF-NDT1在荧光识别甲醛方面有潜在的应用前景.     

HArF和HNO二聚体相互作用氢键的理论研究

The hydrogen bonding interaction of 1:1 dimer formed between HNO and HArF molecule has been completely investigated in the present study using Second-order M?ller-Plesset Perturbation (MP2) method in conjunction with 6-311+G**, 6-311++G** and 6-311++G(2d,2p) basis sets. The standard and CP-corrected calculations have been employed to determine the equilibrium structures, the vibrational frequencies and interaction energies. The interaction energies of the dimers were also calculated at G2MP2 level. Two stable structures are found as the minima. Dimer I(H···F)is a five-membered cyclic hydrogen bonded structure and is more stable than the Dimer II(H···O). The blue-shifted N-H···F hydrogen bond is confirmed with standard and CP-corrected calculations by the MP2 and DFT methods in conjunction with different basis sets. The results obtained at MP2 in conjunction with different basis sets show there is a red-shifted hydrogen bond (Ar-H···O) in the Dimer II(H···O). The topological and electronic properties, the origin of red- and blue-shifted hydrogen bonds were investigated at MP2/6-311++G(2d,2p) with CP corrected calculations. From the NBO analysis, the reasonable explanations for the red- and blue-shifted hydrogen bonds were proposed.     

Ab initio Hartree-Fock investigation of 1-H-pyrrolo[3,2-b]pyridine-3-yl acetic acid

The potential energy surface of 1-H-pyrrolo[3,2-b]pyridine-3-yl acetic acid has been investigated via RIIF/6-31G* calculations. The stationary points and reaction paths for syn orientation of the COOH group were determined and are compared with those of the derivatives of 3-indole acetic acid, which act as plant growth hormones. 1-H-pyrrolo[3,2-b]pyridine-3-yl acetic acid forms a kinetically stable conformer with a strong intramolecular hydrogen bond, in which the COOH group is in anti orientation. The influence of this hydrogen bond on bond lengths and vibration frequencies is described.     

Quantum Study on the Hydrogen Bonding Interaction of Luteolin-（CH_3OH）_n

The optimized geometries and vibration frequencies of luteolin,methanol and luteolin-(CH3OH)n complexes have been investigated by density functional theory using B3LYP method.Four stable luteolin-CH3OH complexes,six stable luteolin-(CH3OH)2 complexes and four stable luteolin-(CH3OH)3 complexes have been obtained.The theories of atoms in molecules(AIM) and natural bond orbital(NBO) have been used to analyze the hydrogen bonds of these compounds,and their interaction energies corrected by basis set superposition error are between-8.046 and-76.124 kJ/mol.The calculation results indicate strong hydrogen bonding interactions in the luteolin-(CH3OH)n complexes.Then the nuclear magnetic resonance(NMR) and electronic absorption spectrum of luteolin have been calculated,and the results are in agreement with the experimental data.     

Theoretical and Experimental Studies on a Metallorganic Complex of (Isopropylxanthato)(Phenyl)Mercury(I) [Hg(I)(C<Subscript>6</Subscript>H<Subscript>5</Subscript>)(C<Subscript>4</Subscript>H<Subscript>7</Subscript>OS<Subscript>2</Subscript>)]

The title compound, (isopropylxanthato)(phenyl)mercury(I), was synthesized and characterized by elemental analysis, IR and thermogravimetric analysis. Density functional theory (DFT) method calculations were performed at B3LYP/CEP-121G and B3LYP/CEP-31G levels of theory, respectively. Vibrational frequencies were predicted, assigned, compared with the experimental values, and they are supported each other. The calculated results show that the strength of bond Hg—C is stronger than that of Hg—S, which is good agreement with the experimental data. The calculations of the second order optical nonlinearity and electronic absorption spectra are also performed.     

Effect of cooperative hydrogen bonding in azo-hydrazone tautomerism of azo dyes

Azo-hydrazone tautomerism in azo dyes has been modeled by using density functional theory (DFT) at the B3LYP/6-31+G(d,p) level of theory. The most stable tautomer was determined both for model compounds and for azo dyes Acid Orange 7 and Solvent Yellow 14. The effects of the sulfonate group substitution and the replacement of the phenyl group with naphthyl on the tautomer stability and on the behavior in solvent have been discussed. Intramolecular hydrogen bond energies have been estimated for the azo and hydrazone tautomers to derive a relationship between the tautomer stability and the hydrogen bond strength. The transition structures for proton transfer displayed resonance assisted strong hydrogen bonding properties within the framework of the electrostatic-covalent hydrogen bond model (ECHBM). Evolution of the intramolecular hydrogen bond with changing structural and environmental factors during the tautomeric conversion process has been studied extensively by means of the atoms-in-molecules (AIM) analysis of the electron density. The bulk solvent effect was examined using the self-consistent reaction field model. Special solute-solvent interactions were further investigated by means of quantum mechanical calculations after defining the first-solvation shell by molecular dynamics simulations. The effect of cooperative hydrogen bonding with solvent molecules on the tautomer stability has been discussed.     

Fourier transform infrared and Raman spectra, vibrational assignment and density functional theory calculations of naphthazarin

FT Raman and FTIR spectra of Naphthazarin (5,8-dihydroxy-1,4-naphthoquinone) and its deuterated analogue are recorded. Comparison between the spectra obtained by two techniques, a series of density functional theory (DFT) calculations and the spectral behavior upon deuteration were used for the assignment of the vibrational spectra of this compound. The calculated vibrational frequencies by the B3LYP, B3PW91, G96LYP, G96P86, and MPWLYP density functionals are generally consistent with the observed spectra. Infrared and Raman vibrational transitions predicted by B3LYP/6-311++G** are reported for the titled compound and its deuterated analogous and the assignments are discussed. All experimental and theoretical results support a relatively weak hydrogen bond in naphthazarin (NZ), compared with that in the enol form of normal beta-diketones. The observed nuOH/nuOD and gammaOH/gammaOD appear at about 3060/2220 and 790/560 cm(-1), respectively, which are consistent with the calculated hydrogen bond geometry and proton chemical shift results. Two bands at about 350 and 290 cm(-1) are assigned to the O...O stretching modes belong to A1 and B2 species, respectively.     

An approach to estimate the energy and strength of the intramolecular hydrogen bond in different conformers of 4‐methylamino‐3‐penten‐2‐one

The molecular structure and intramolecular hydrogen bond energy of 32 conformers of 4‐methylamino‐3‐penten‐2‐one were investigated at MP2 and B3LYP levels of theory using the standard 6–31G** basis set and AIM analyses. Furthermore, calculations for all the possible conformations of 4‐methylamino‐3‐penten‐2‐one in water solution were also carried out at B3LYP/6–31G** level of theory. The calculated geometrical parameters and conformational analyses in gas phase and water solution show that the ketoamine conformers of this compound are more stable than the other conformers (i.e., enolimine and ketoimine). This stability is mainly due to the formation of a strong N? H···O intramolecular hydrogen bond, which is assisted by π‐electrons resonance. Hydrogen bond energies for all conformers of 4‐methylamino‐3‐penten‐2‐one were obtained from the related rotamers method. The nature of intramolecular hydrogen bond existing within 4‐methylamino‐3‐penten‐2‐one has been investigated by means of the Bader theory of atoms in molecules, which is based on topological properties of the electron density. The results of these calculations support the results which obtained by related rotamers method. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

The influence of CH…π interaction on hydrogen bonding ability of –CONH<Subscript>2</Subscript> functional group of benzamide

Interplay between CH…π and hydrogen bond interactions of benzamide has been investigated by quantum mechanical calculations. The effect of the substituents on geometrical parameters has also been studied at the B3LYP level with 6-311++G(d,p) basis set. The electron-withdrawing substituents enhance the total interaction energy of the complexes. The results indicated that the cooperativity of interactions leads to extra stability of the ternary complexes. The CH…π interaction and the hydrogen bond energies have been estimated using the electron densities calculated by the atoms in molecules (AIM) method at hydrogen bond critical points. The strength of hydrogen bonding increases in the presence of CH…π interaction in the ternary complexes. The effect of CH…π interaction on the hydrogen bond interaction has also been studied by the natural bond orbital, AIM and the molecular electrostatic potential analyses.     

取代基对N—H…O＝C氢键三聚体中氢键强度的影响

使用MP2方法研究了氢键三聚体中N-H…O=C氢键强度,探讨了氢键受体分子中不同取代基对N-H…O=C氢键强度的影响.研究表明,不同取代基对氢键三聚体中N-H…O=C氢键强度的影响是不同的:取代基为供电子基团,氢键键长r(H…O)缩短,氢键强度增强;取代基为吸电子基团,氢键键长r(H…O)伸长,氢键强度减弱.自然键轨道(NBO)分析表明,N-H…O=C氢键强度越强,氢键中氢原子的正电荷越多,氧原子的负电荷越多,质子供体和受体分子间的电荷转移越多.供电子基团使N-H…O=C氢键中氧原子的孤对电子n(O)对N-H的反键轨道σ~*(N-H)的二阶相互作用稳定化能增加,吸电子基团使这种二阶相互作用稳定化能减小.取代基对与其相近的N-H…O=C氢键影响更大.