Reaction intermediates of methanol synthesis and the water–gas-shift reaction on the ZnO(0001) surface

The polar Zn-ZnO(0001) surface is involved in the catalysis of methanol synthesis and the water–gas-shift reaction. We use density functional theory calculations to explore the favorable binding geometries and energies of adsorption of several molecular species relevant to these reactions, namely carbon monoxide (CO), carbon dioxide (CO₂), water (H₂O) and methanol (CH₃OH). We also consider several proposed reaction intermediates, including hydroxymethyl (CH₂OH), methoxyl (CH₃), formaldehyde (CH₂O), methyl (CH₃), methylene (CH₂), formic acid (HCOOH), formate (HCOO), formyl (HCO), hydroxyl (OH), oxygen (O) and hydrogen (H). For each, we identify the preferred binding geometry at a coverage of 1/4 monolayers (ML), and report calculated vibrational frequencies that could aid in the identification of these species in experiment. We further explore the effects on the binding energy when the adsorbate coverage is lowered to 1/9 and 1/16 ML.     

Torsional refilling transitions in tea-pumped CH3OH fir lasers with associated high-resolution fir spectra

It is proposed that a number of the high-frequency far-infrared (FIR) laser lines observed when CH₃OH is optically pumped by high-power CO₂ TEA lasers can be identified as refilling torsional transitions within the vibrational ground state. Assignments are presented for 8 such TEA-pump/FIR-laser refilling systems. To provide support for the assigned laser frequencies, high-resolution Fourier transform FIR spectra of CH₃OH have been obtained and partially analyzed in the torsional transition region.     

Structures and Vibrational Spectra of the Hydrogen-Bonded Complexes Between Nitrous Acid and Acetone: Ab Initio and DFT Studies

ABSTRACT

The structures, stability, and vibrational spectra of the binary complexes formed between acetone and nitrous (trans and cis) acid have been investigated using ab initio calculations at the SCF and MP2 levels and B3LYP calculations with 6-311++G(d,p) basis set. Full geometry optimization was made for the complexes studied. It was established that the complex (CH₃)₂CO···HONO-trans is more stable than the complex (CH₃)₂CO···HONO-cis by 0.5–0.8 kcal·mol^?1. The accuracy of the calculations has 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/6-311++G(d,p) calculations are very near to the results, obtained with MP2/6-311++G(d,p). The calculated frequency shift Δν(O[sbnd]H) for the complex (CH₃)₂CO···HONO-trans (1A) is larger than for the complex (CH₃)₂CO···HONO-cis (1B). In the same time the intensity of this vibration increases dramatically upon hydrogen bonding. The calculated increase for the complex 1A is up to 15 times and for the complex 1B is up to 30 times. The changes in the vibrational characteristics (vibrational frequencies and infrared intensities) of (CH₃)₂CO upon the complexation are more insignificant than the changes in the vibrational characteristics of HONO-trans and HONO-cis.     

Pure Rotational Raman Spectra of Vapor Phase Methanols

Abstract

The rotational Raman spectra of four vapor phase isotopic methanols, CH₃OH, CH₃OD, CD₃OH and CD₃OD, have been reported for the first time in the wavenumber regions from 5 to 100–120 cm^?1. The major parts of the spectra consist of bands equispaced at 3.19, 3.04, 2.56 and 2.46 cm^?1 intervals, respectively, and have been interpreted as the pure rotational S-branch transitions.     

Characterization of the adsorption and decomposition of methanol on Ni(110)

The chemisorption, condensation, desorption, and decomposition of methanol, both CH₃OH and CH₃OD, on a clean Ni(110) surface have been characterized using high resolution electron energy loss spectroscopy, temperature programmed reaction spectroscopy, and low energy electron diffraction. The vibrational spectrum of the saturated chemisorbed layer, 7.4 × 10¹⁴ molecules cm^?2, is almost identical to the infrared spectrum of liquid or solid methanol. Condensation of multilayers of methanol is facile at 80 K. The only quasi-stable intermediate isolated during the decomposition is a methoxy species, CH₃O, which decomposes thermally to CO and H. The evolution of both CO and H₂ occurs in desorption limited processes.     

光电子成像研究AgOCH3-和Ag-(CH3OH)x (x=1, 2)

用光电子成像技术和从头算法研究Ag^-(CH₃OH)_x (x=1, 2)和AgOCH₃^-. 从AgOCH₃^-振动分辨的光电子谱得 到AgOCH₃^-的绝热和垂直电离能分别为1.29(2)和1.34(2) eV. Ag^-(CH₃OH)_{1,2相似文献}   

全维高精度势能面上F+CH3OH反应的产物振动态分布

甲醇与氟原子之间的抽氢反应可以生成HF和CH₃O、CH₂OH自由基等产物. 该反应在环境化学、燃烧化学、辐射化学和星际化学中都非常重要. 基于之前构建的全维高精度势能面,本文采用准经典轨线方法研究了该典型反应的动力学. 特别是使用正则模式分析方法确定了多原子产物CH₃O和CH₂OH的振动态分布. 研究发现,当反应物处于振转基态时,CH₃O和CH₂OH主要分布在基态. 当反应物CH₃OH的OH伸缩模式激发为第一激发态时,产物CH₂OH的OH伸缩模式、扭转模式、H₂CO 面外弯曲模式及其组合会被有效激发. 在两条通道中,可用能量大部分都流入HF的振动能和产物的平动能,而自由基产物CH₃O或CH₂OH只得到非常少的能量,与实验结果一致,这也表明了自由基的旁观者性质.     

Betulin and its natural resource as potential anticancer drug candidate seen by FT‐Raman and FT‐IR spectroscopy

The Fourier transform Raman and IR spectra of betulin (lup‐20(29)‐ene‐3β,28‐diol) crystalline powder were recorded and analyzed. The vibrational wavenumbers and the corresponding vibrational assignments were theoretically studied using the Gaussian 03 package. The calculated vibrational wavenumbers with the B3LYP density functionals are generally consistent with the observed spectra. A complete vibrational characterization of betulin modes has been proposed here for the first time. Based on the vibrational analysis, two direct applications of the results have been described. It was shown that the outer bark of Betula Pendula Roth (the birch tree) contains betulin as a major component along with minor amounts of betulinic acid (BA), lupeol and other pentacyclic triterpenes derivatives. Since the major disadvantage of betulin is its low solubility, giving rise to serious problems in making pharmaceutical formulations, several guest–host type of complexes of betulin–cyclodextrins have been prepared and analyzed using FT‐Raman spectroscopy. Based on the vibrational analysis, it was concluded that the OH and CH₂OH functional groups are free from chemical interactions with the cyclodextrin cavity. Copyright © 2010 John Wiley & Sons, Ltd.     

二氧化钛薄膜表面甲醇吸附的和频振动光谱

自行搭建了用于研究表面光催化的宽带红外和频振动光谱并可以原位紫外光激发的装置. 利用自制的结构紧凑小巧的高真空样品池,可以在10 kPa氧气氛围下经原位紫外光照除掉 射频磁控溅射制备的二氧化钛薄膜表面的有机污染物. 通过在室温下改变甲醇气压和指认吸附在薄膜表面的甲醇的和频振动光谱,发现薄膜表面有两种吸附的甲醇,分子形式吸附的甲醇(CH₃OH)和解离吸附的甲醇(CH₃O). 当甲醇的覆盖度由低变高时,分子形式吸附的甲醇的CH₃的对称伸缩振动和费米共振峰红移了6～8 cm^-1. 真空下,薄膜表面的甲氧基和表面的氢原子可以重新结合并以甲醇分子的形式脱附. 研究表明二氧化钛薄膜体系存在两个平衡：气相甲醇和表面吸附的甲醇分子之间,以及表面吸附的甲醇分子和甲氧基之间.     

Confirmation of far infrared laser assignments from CH3-deformation and CH3-rocking states of optically pumped methanol

High-resolution Fourier transform spectroscopy has been applied to confirm previously proposed assignments for nine far infrared (FIR) laser lines from the CH₃-deformation state of CH₃OH and one line from the CH₃-rocking state. Accurate frequencies are deduced for the observed and other predicted FIR laser transitions. FIR torsional branch frequencies in the ground state which were used in the confirmation are presented. Comments are also made on the OH-bending mode of CH₃OH.     

线性和非线性光谱研究甲醇分子对生物膜的微扰作用 (cited: 3)

利用和频光谱并结合衰减全反射傅立叶红外光谱技术研究了甲醇和1,2-dimyristoyl-d54-sn-glycero-3-phosphocholine (d54-DMPC)磷脂双层膜之间的相互作用. 研究结果表明甲醇与生物膜作用后,嵌入到磷脂分子头部的胺基和磷酸基间的空间内,并与磷脂分子头部甲基以及与胺基附近水分子采用相似的取向方向. 嵌入磷脂分子头部的甲醇分子能扰动磷脂分子的整个疏水碳链.     

Hydroxyl end groups influence in vibrational and transport properties in polymer/monomer solutions: the PEO/EG case

A study has been made of vibrational properties in ethylene glycol (EG; H(OCH₂CH₂)OH) and EG monomethyl ether (EGmE; CH₃(OCH₂CH₂)OH) in solution together with poly(ethylene oxide) (PEO; H(OCH₂CH₂)_n,OH) at different concentrations, performed by Fourier transform infrared absorbance (FT-IR) spectroscopy. The results ae compared with previous viscometry and photon correlation spectroscopy (PCS) studies, using EG dimethyl ether (EGdE; CH₃(OCH₂CH₂)OCH₃) as solvent as well. These homologous systems differ from each other in the number of OH end groups, in particular two for EG, one for EgmE and zero for EGdE. Combining analysis of the vibrational and transport properties of EG, EGmE and EGdE in solution with PEO over a wide range of concentration made it possible to check the quality (good theta or poor) of these three different solvents and the role played by the hydrogen bond in the various solute-solvent interaction mechanisms, resulting in the well known de Gennes scaling law.     

The oscillator strengths for C1s and O1s excitation of some saturated and unsaturated organic alcohols,acids and esters

Electron energy loss Spectroscopy (ISEELS) under dipole scattering conditions is used to obtain the carbon and oxygen K-shell oscillator strength spectra of methanol (CH₃OH), propanol (CH₃CH₂CH₂OH), propenol (CH₂=CHCH₂OH), propargyl alcohol (HC≡CCH₂OH), propanoic acid (CH₃CH₂COOH), acrylic acid (CH₂=CHCOOH) and propiolic acid (HC≡CCOOH). A detailed interpretation of these spectra is presented, along with a comparison with the NEXAFS spectra of multilayers of these molecules adsorbed on a Si(111) surface, as recently reported by Outka et al. (Surf. Sci., 185 (1987) 53). Good agreement is found between the multilayer NEXAFS and the gas phase ISEEL spectra, except for the carboxylic acids which differ dramatically in the discrete portion of the O1s spectrum. Possible origins for this difference are discussed. The C1s and O1s spectra of methyl formate (HCOOCH₃) are also reported and interpreted in comparison with the spectra of formic acid and methanol.     

Double-stranded helical lanthanide(III) supramolecular networks with rigid diimine ligands: Synthesis, structure, and physical properties

Two lanthanide coordination complexes [Nd(NO₃)₃(CH₃OH)₂(4,4′-bipy)₂] (1) (4,4′-bipy=4,4′-bipyridine) and [4,4′-Hbipy][La(NO₃)₄(H₂O)₂(4,4′-bipy)] (2), with a salt of cationic diprotonated 4,4′-bipy, [2(4,4′-H₂bipy)][4(NO₃)] (3), have been identified and isolated from a methanol solution of Ln(NO₃)₃·6H₂O, 4,4′-bipyridine and pyrazine in 1:2:1 ratio. Their structures have been determined by single-crystal X-ray diffraction analyses, which reveal that 1 has an interesting three-dimensional supramolecular architecture containing 2₁ double-stranded helical chains through hydrogen bonding and π–π interactions, while 2 and 3 have well defined infinite chiral 3D open networks that undergo self-interpenetration. The electrospray ionization mass spectra (ESI-MS) indicate that the covalent complex has higher stability than the electrostatic bonding one. ESI-MS/MS of these ions reveal that the Ln–O bond forms a stronger coordinated bonding than that of Ln–N system and the nitrate anion remains bound to the lanthanide centers after complete dissociation in methanol solution.     

A review of optically pumped far-infrared laser lines from methanol isotopes

The technique of optical pumping in polar molecules is the most efficient for Far-Infrared (FIR) laser generation, providing also a versatile and powerful tool for molecular spectroscopy in this spectral region. Methanol (CH₃OH) and its isotopic varieties are the best media for optically pumped FIR laser, with over thousand lines observed, and the most widely used for investigations and applications. In this sense, it is important organize and make available catalogues of FIR laser lines as complete as possible. Since the last critical reviews of 1984 [1] on methanol and its isotopic varieties [2,3,4], over hundred papers have been published dealing with hundreds of new FIR laser lines. In 1992 a review of FIR laser lines from CH₃OH was presented [5]. In this communication we extend this work to the other methanol isotopes, namely CH₃OD, CD₃OH, CD₃OD,¹³CH₃OH,¹³CD₃OH,¹³CD₃OD, CH₃ ¹⁸OH, CH₂DOH, CHD₂OH and CH₂DOD.Work supported by FAPESP, CNPq, FAEP-Brasil, and CNR-Italia     

Sub-millimeter wave spectroscopy of CHD2OH: a-type and asymmetry induced c-type transitions in the lowest three torsional sub-levels

The sub-millimeter wave (SMMW) spectral measurements using a fast scan backward wave oscillator based spectrometer have been carried out for asymmetrically deuterated methanol CHD₂OH (Methanol-D₂). Transition frequencies have an estimated uncertainty of about ±50 kHz. Albeit the complexity in the spectra, assignments were possible for a large number of a-type (ΔK = 0) transitions. In the course of the assignment process a strong c-type (ΔK = 1) Q-branch connecting two states of different symmetry species has been identified. This Q-branch assignment is significant because it is forbidden in the normal parent species CH₃OH. It becomes allowed in the current species due to the effects of the asymmetry introduced by the off-axis deuterium in the hindering potential to the internal rotation in the molecule. The assignments are rigorously confirmed using combination relations which required the measurement of some other related lines. To our knowledge this is the first time such symmetry breaking transitions are reported in CHD₂OH and in fact this is the first time the SMMW spectrum of CHD₂OH is being reported. Detailed spectral study of this molecule in the IR and FIR regions is in progress and will be reported elsewhere. Detailed study of the identification optically pumped FIR laser line is underway.     

Vibrational spectra of the tetramethylpnikogenonium ions

The tetramethylpnikogenonium ions (CH₃)₄X⁺ (X = N, P, As, Sb) have been studied by infrared and Raman spectroscopy. Additionally, their structures and vibrational frequencies were ab initio calculated at the HF/6-31+G* and for (CH₃)₄Sb⁺ at the HF/6-31+G*/LANL2DZ level of theory. For the tetrahedral cations an assignment of the vibrational frequencies is discussed on the basis of a comparison of calculated and measured frequencies.     

Anharmonic force field for methanol

An ab initio quartic anharmonic force field for methanol has been calculated at the equilibrium position using the CCSD(T) method for the structure and the harmonic potential energy surface, and the MP4(SDQ) method for the anharmonic part of the surface. A triple zeta basis set was employed with symmetrized curvilinear internal valence coordinates in all calculations. The internal coordinate force field constants have been transformed into force constants in the dimensionless normal coordinate representation for various isotopomers. Vibrational term values for CH₃OH, CH₃OD, CD₃OH, and CD₃OD have been obtained using second order perturbation theory. Particular care has been devoted to the inclusion of Fermi resonance interactions between different vibrational states. A good accuracy has been achieved in the calculation of the fundamentals for all the isotopomers, the mean absolute error being 5.8 cm^?1.     

The adiabatic approximation as a diagnostic tool for torsion-vibration dynamics

The adiabatic separation of large-amplitude torsional motion from small-amplitude vibrations is applied as an aid in interpreting the results of fully coupled quantum calculations on a model methanol Hamiltonian. Comparison is made with prior work on nitromethane [D. Cavagnat, L. Lespade, J. Chem. Phys. 106 (1997) 7946]. Even though the torsional potentials are very different, both molecules show a transition from adiabatic to diabatic behavior when the CH stretch is excited to ν_CH = 4 or higher. In the adiabatic approximation, the effective torsional potentials for the various CH stretch vibrational states do not cross, but the CH vibrational amplitude moves from one bond to the next as a function of torsional angle. In the diabatic approximation, the effective torsional potentials do cross, but the distribution of the CH vibrational amplitude remains approximately constant in the vicinity of the crossing. The transition to diabatic behavior is promoted by the normal mode to local mode transition, and the relevant adiabatic and diabatic effective torsional potentials are determined by the torsion-vibration coupling. The torsion-vibration couplings in the four overtone manifolds considered (methanol OH, CH, nitromethane CH, and hydrogen peroxide OH) are large, reaching 265-500 cm⁻¹ by ν_XH = 6, and are of generally similar magnitude. The largest torsion-vibration couplings involve the first Fourier term in the torsional angle (cosγ for the CH stretch in methanol and the OH stretch in HOOH), whereas higher Fourier terms (cos2γ in nitromethane and cos3γ for the OH stretch of methanol) result in somewhat weaker coupling. Nonadiabatic matrix elements in methanol couple the torsional and vibrational energies and they exhibit a slow fall-off with coupling order.