Influence of intermolecular amide hydrogen bonding on the geometry, atomic charges, and spectral modes of acetanilide: An ab initio study

Acetanilide, a compound of pharmaceutical importance possessing pain-relieving properties due to its blocking the pulse dissipating along the nerve fiber, is subjected to vibrational spectral investigation using NIR FT Raman, FT-IR, and SERS. The geometry, Mulliken charges, and vibrational spectrum of acetanilide have been computed using the Hartree-Fock theory and density functional theory employing the 6-31G (d) basis set. To investigate the influence of intermolecular amide hydrogen bonding, the geometry, charge distribution, and vibrational spectrum of the acetanilide dimer have been computed at the HF/6-31G (d) level. The computed geometries reveal that the acetanilide molecule is planar, while twisting of the secondary amide group with respect to the phenyl ring is found upon hydrogen bonding. The trans isomerism and “amido” form of the secondary amide, hyperconjugation of the C=O group with the adjacent C-C bond, and donor-acceptor interaction have been investigated using computed geometry. The carbonyl stretching band position is found to be influenced by the tendency of the phenyl ring to withdraw nitrogen lone pair, intermolecular hydrogen bonding, conjugation, and hyperconjugation. A decrease in the NH and C=O bond orders and increase in the C-N bond orders due to donor-acceptor interaction can be observed in the vibrational spectra. The SERS spectral analysis reveals that the flat orientation of the molecule on the adsorption plane is preferred.     

Quantum chemical insight into molecular structure,density functional theory calculations,vibrational dynamics,natural population analysis,Hirshfeld analysis,and molecular docking approach to chalcone 1-4-bromophenyl-3-(2-methoxyphenyl)prop-2-en-1-one

The structure of the novel chalcone 1-4-bromophenyl-3-(2-methoxyphenyl)prop-2-en-1-one has been characterized by Fourier transform infrared and Fourier transform Raman. Density functional theory with Becke, 3-parameter, Lee-Yang-Parr functional was used for the optimization of geometry. The comprehensive assignments of the vibrational spectra have been performed with the aid of normal coordinate analysis. Stability of the molecule and intra/intermolecular charge transfer have been analyzed using natural bond orbital analysis. The existence of intermolecular C-H?O, blueshifted hydrogen bond was investigated by bond length variation. Hirshfeld and two-dimensional fingerprint plot analyses have been performed to study the nature of interactions present in the molecule. The docked complex gives a constancy of ?8.2?kcal/mol toward the androgen receptor.     

甲醇的高压拉曼光谱研究

研究了甲醇在温度301K、压力169．2～713．8MPa下的拉曼特征。其中νCH区伸缩振动随压力增大，拉曼位移向高频方向移动，说明C-H键键能在增大；而νOH区伸缩振动随压力增大，拉曼位移则向低频方向移动，表明氢键对O-H基团的影响大于压力效应。另外，O-H伸缩振动峰的相对面积随压力的增大而减小，说明对C-H键而言，O-H键总强度是减弱的。     

Vibration states of hydrogen on tungsten

The vibrational excitation of hydrogen adsorbed on the low-index faces of tungsten have been investigated using electron energy-loss spectroscopy. The results indicate the same vibrational force constant in “on-top” sites independent of substrate-atom geometrical environment.     

β-胡萝卜素分子的黄琨因子的温度特性

β-胡萝卜素具有光采集、光防护功能, 又是重要的光电材料, 它在外场下的分子结构和性能变化既有理论意义也有应用价值。测量了β-胡萝卜素在环己醇中68～26 ℃温度范围内的紫外-可见吸收、拉曼光谱。实验结果表明随着温度的降低, 黄琨因子和碳碳键每个振动模的电子-声子耦合常数减小, 紫外-可见吸收光谱红移, 碳碳键拉曼散射截面增加。用线性链状多烯分子的“相干弱阻尼电子-晶格振动模型”、“有效共轭长度模型”等理论给予了解释。随着温度的降低,β-胡萝卜素分子的热无序减小,分子结构有序性增加,π电子离域扩展,有效共轭长度增加,导致紫外-可见吸收光谱红移和强的拉曼活性。相干弱阻尼电子-晶格振动增强,使碳碳键拉曼散射截面增加。引用带有量纲的电子-声子相互作用常数,既可以与黄昆因子建立关系式,计算出碳碳键每个振动模的数值,也可以表征分子的有效共轭长度,π电子离域程度及拉曼散射截面的大小等。     

密度泛函理论研究过渡金属对吡啶的拉曼光谱强度的影响

本文采用杂化密度泛函理论计算了过渡金属M -Py分子的基态振动频率和拉曼光谱强度。计算结果表明过渡金属对Py分子的振动频率影响较小 ,但对Py分子的A1 振动模式的拉曼谱强度影响较大。对于A1 对称性的非C -H伸缩振动模 ,吡啶分子环呼吸振动和高频的C -C对称伸缩振动有较大的拉曼散射因子 ,我们还将此结果与典型的SERS活性金属 (铜族金属 )进行了比较     

Temperature-Dependent Raman Study on Vibrational Modes in LiTaO3

In this paper the results of temperature-dependent Raman study on the vibrational modes in LiTaO₃ crystals are presented. It is found that the two low-frequency A₁ modes show significant changes during the temperature changing process. “Modes softening” and “frequency-repulsion” effect was observed and dicussed.     

Investigation of hydrogen bonding in neat dimethyl sulfoxide and binary mixture (dimethyl sulfoxide + water) by concentration-dependent Raman study and ab initio calculation

In this study,our vibrational spectroscopic analysis is made on hydrogen-bonding between dimethyl sulfoxide and water comprises both experimental Raman spectra and ab initio calculations on structures of various dimethyl sulfoxide/water clusters with increasing water content.The Raman peak position of the v(S=O) stretching mode of dimethyl sulfoxide serves as a probe for monitoring the degree of hydrogen-bonding between dimethyl sulfoxide and water.In addition,the two vibrational modes,namely,the CH 3 symmetric stretching mode and the CH 3 asymmetric stretching mode have been analysed under different concentrations.We relate the computational results to the experimental vibrational wavenumber trends that are observed in our concentration-dependent Raman study.The combination of experimental Raman data with ab initio calculation leads to a better knowledge of the nature of the hydrogen bonding and the structures of the hydrogen-bonded complexes studied.     

Vibrational spectra and scaled quantum chemical studies of the structure of Martius yellow sodium salt monohydrate

The FT‐IR and Raman spectra of Martius Yellow sodium salt Monohydrate (MYM) [2, 4‐dinitro‐1‐naphthol sodium salt] in solid‐phase have been measured. The geometry, intramolecular hydrogen bonding and harmonic vibrational wavenumbers of MYM have been investigated with the help of B3LYP density functional theory (DFT) methods. The detailed interpretation of the vibrational spectra has been carried out with the aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology (SQMFF). The existence of intramolecular C H···O improper, blue‐shifted hydrogen bonding was investigated by means of the NBO analysis. The infrared and Raman spectra were predicted theoretically from the calculated intensities. The observed and the calculated spectra were found to be in good agreement. Copyright © 2009 John Wiley & Sons, Ltd.     

Hydrogen bonding in nitrofurantoin polymorphs: a computation‐assisted spectroscopic study

The importance of hydrogen‐bond formation in the molecular packing arrangements of two anhydrous forms of nitrofurantoin is investigated, combining computational methods and spectroscopic data. The overall results indicate, as expected, that the vibrational modes related to the CO, N H and C H groups are strongly affected by intermolecular hydrogen‐bond formation. Moreover, the importance of weak C‐H···O interactions in conferring additional stability to molecular associations in biological systems is evidenced in this study. The complete assignment of the Raman and infrared spectra of both polymorphs is accomplished by means of a computationally based methodology, which accounts for the effects of intermolecular interactions in the crystal. The vibrational shifts due to crystal packing interactions are evaluated from DFT calculations for a set of suitable molecular pairs, using the B3LYP/6‐31G* approach. This methodology provides an answer to the current demand for a reliable and complete assignment of the vibrational spectra of pharmaceutically active compounds such as nitrofurantoin. Copyright © 2009 John Wiley & Sons, Ltd.     

FT‐IR,FT‐Raman and DFT calculations of the salicylanilide derivate 4‐chloro‐2‐(4‐bromophenylcarbamoyl)phenyl acetate

FT‐IR and FT‐Raman spectra of 4‐chloro‐2‐(4‐bromophenylcarbamoyl)phenyl acetate were recorded and analyzed. The vibrational wavenumbers and corresponding vibrational assignments were examined theoretically using the Gaussian03 set of quantum chemistry codes. The red shift of the NH stretching wavenumber in the infrared (IR) spectrum from the computed wavenumber indicates the weakening of the NH bond resulting in proton transfer to the neighbouring oxygen atom. The simultaneous IR and Raman activations of the CO stretching mode give the charge transfer interaction through a π‐conjugated path. Optimized geometrical parameters of the title compound are in agreement with similar reported structures. From the optimized structure, it is clear that the hydrogen bonding decreases the double bond character of CO bond and increases the double bond character of the C N bonds. The first hyperpolarizability, predicted infrared intensities and Raman activities are reported. The calculated first hyperpolarizability is comparable with the reported values of similar derivatives and is an attractive object for future studies of non‐linear optics. The assignments of the normal modes are done by potential energy distribution (PED) calculations. Copyright © 2009 John Wiley & Sons, Ltd.     

Theoretical and Experimental Study of the Conformation and Vibrational Frequencies of N‐Acetyl‐L‐alanine and N‐Acetyl‐L‐alaninate

The vibrational frequencies of N‐acetyl‐L‐alanine (NAAL), its potassium salt (NAALK) and its free anionic form (NAAL^?) are calculated using density functional theory (B3LYP) combined with the 6‐311 + + G(d,p) basis set. The experimental Raman spectrum of solid NAALK and the scaling factors for calculated values are discussed as well. The three species are characterized by intramolecular NH…O hydrogen bonds leading to the formation of a five‐membered ring. As indicated by the intramolecular (N)H…O distances and by the ν(NH) frequencies, the strength of the intramolecular hydrogen bond is ordered as follows: NAAL^? < NAALK < NAAL^?. Owing to their difference in the coupling with other vibrational modes, the in‐plane and out‐of‐plane vibrations do not reflect the strength of the hydrogen bond.     

Hydrogen local vibrational modes in zinc oxide

Using Raman backscattering spectroscopy we have observed six local vibrational modes in as-grown state-of-the-art nominally undoped zinc oxide single crystals. The local vibrational modes are located at nu=2854, 2890, 2918, 2948, 2988, and 3096 cm(-1). Some specimens were annealed up to 950 degrees C to remove hydrogen. A subsequent Raman backscattering measurement revealed that the local vibrational modes disappeared. This establishes that the observed local vibrational modes are caused by the presence of hydrogen in the ZnO crystals.     

Thermal loss mechanism in the generation of multifrequency laser emission via stimulated Raman scattering and four-wave Raman mixing studied by photothermal refraction spectroscopy

The heat produced in conjunction with the processes of stimulated Raman scattering and four-wave Raman mixing in hydrogen was measured by photothermal refraction spectroscopy. Many vibrational, rotational, and vibrationally shifted rotational Raman lines are exclusively/simultaneously generated by changing the polarization of the laser beam and the hydrogen pressure. Thermal loss occurs predominantly from vibrational Raman scattering, which can be ascribed to a large Raman shift frequency of 4155 cm^-1 for the vibrational transition. In contrast to stimulated Raman scattering, little or no thermal loss is observable during the process of four-wave Raman mixing. Received: 12 April 1999 / Revised version: 12 July 1999 / Published online: 20 October 1999     

Effect of hydrogen bonding in the vibrational spectra of trans‐cinnamic acid

A computationally‐assisted methodology to assign the vibrational spectra of molecular materials (PiMM) has been successfully applied to the Raman and infrared (IR) spectra of trans‐cinnamic acid (t‐CIA) in the solid state. The effects of molecular association through O H···O hydrogen‐bonding in both the wavenumber and the intensity of the bands are accurately described by a single dimer structure. This supports the discrimination between the possible conformers in the solid, the complete evaluation of hydrogen‐bonding effects, and the full assignment of the vibrational spectra of t‐CIA. Copyright © 2008 John Wiley & Sons, Ltd.     

NIR‐FT Raman and FT‐IR spectral investigations of the nonlinear optical chromophore p‐bromoacetanilide

Vibrational spectral analysis of the hydrogen‐bonded nonlinear optical (NLO) material p‐bromo acetanilide (PBA) was carried out using NIR‐FT‐Raman and FT‐IR spectroscopy. Ab initio molecular orbital computations were performed at HF/6‐31G (d) level to derive equilibrium geometry, vibrational wavenumbers, intensities and first hyperpolarizability. The lowering of the imino stretching wavenumbers suggests the existence of strong intermolecular N H···O hydrogen bonding, which was substantiated by the natural bond orbital (NBO) analysis. The vibrational spectra confirm that the charge‐transfer interaction between the  NHCOCH₃ group and—Br through phenyl ring is responsible for simultaneous strong IR and Raman activation of the ring mode 8a. Vibrational analysis indicates that the lowering of stretching wavenumbers of methyl group due to electronic effects simultaneously caused by induction and hyperconjugation is due to the presence of the oxygen atom. The presence of blue‐shifting H‐bonds of CH stretching wavenumbers, simultaneous activation of carbonyl stretching mode, the strong activity of low‐wavenumber H‐bond stretching vibrations and the role of intramolecular charge transfer in making the molecule NLO active have been analyzed on the basis of the vibrational spectral features. Copyright © 2007 John Wiley & Sons, Ltd.     

Crystal and molecular structure of 2‐amino‐5‐chloropyridinium hydrogen selenate—its IR and Raman spectra,DFT calculations and physicochemical properties

The new organic‐inorganic salt, 2‐amino‐5‐chloropyridinium hydrogen selenate, has been synthesised and characterised by means of FT‐IR, FT‐Raman and single crystal X‐ray crystallography. Its vibrational spectra have been discussed on the basis of quantum chemical DFT calculations using the B3LYP/6‐31G(d,p) approach. The crystal and molecular structures have been compared and the role of the intermolecular interactions in this crystal has been analysed. The N HO interactions between the hydrogen atoms of the organic cation and oxygen atoms of hydrogen selenate anion determine the supramolecular arrangement in three‐dimensional space. The possible application of the studied composite material as a Raman laser has been discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Efficient generation of vibrational stimulated Raman emission in the ultraviolet region using a femtosecond pump beam

The third harmonic emission (261 nm, 30 μJ) of a femtosecond Ti:sapphire laser is focused into molecular hydrogen to generate vibrational stimulated Raman emission. High-order emission lines are efficiently generated by using a high-beam-quality nearly-transform-limited laser and high-pressure hydrogen (40 atm) as a Raman medium.     

The influence of Fermi energy on structural and electrical properties of laser crystallized P-doped amorphous silicon

A series of phosphorous-doped hydrogenated amorphous silicon films (a-Si:H) were crystallized using step-by-step laser crystallization process. The structural changes during the sequential crystallization process were detected by Raman measurements. The dehydrogenation was monitored by measuring the Si-H local vibrational modes using Raman spectroscopy and hydrogen effusion measurements. Interestingly, hydrogen bonding is affected by doping of the amorphous material. The influence of doping concentrations, thus the Fermi energy on electronic properties has been investigated employing secondary ion mass spectroscopy (SIMS), dark-conductivity- and Hall-effect measurements. The results from hydrogen effusion are consistent with the results obtained from Raman spectroscopy, Hall-effect- and dark-conductivity measurements.     

拉曼激发激光诱导电子荧光流场测量系统中标记过程的研究

研制了一套拉曼激光发激光诱导电子荧光空气流场测速系统,利用Nd:YAG激光器的二次谐波及其抽运的氧气受激拉曼散射作为标记光源,以ArF准分子激光作为荧光再现光源,并用像增强CCD摄像机（ICCD）记录荧光图像,成功地获得了纯氧及空气中的标记线的荧光图像,并进行了氧气喷流速度测量的初步研究。