<Emphasis Type="Italic">Ab initio</Emphasis> spectroscopic studies of non-rigid molecules: an application to acetic acid

The torsional levels of various isotopologues of acetic acid are determined from an ab initio potential energy surface using a flexible model depending on the OH-torsion and the methyl-torsion coordinates. Previous calculations for CH₃–COOH and CH₃–COOD are review and first theoretical energies of the one-deuterated species CH₂D–COOH are provided. The zero point vibrational energy correction and an exact definition for the methyl-torsional coordinate have been considered. The levels are compared with previous calculations (Senent in Mol Phys 99:1311, 2001) and experimental data (Havey et al. in J Mol Spectrosc 229:151, 2005). Isotopic effects on the torsional barriers and energies are discussed. For CH₂D–COOD, the deuteration splits by 25 cm⁻¹ the zero vibrational energy level.     

Energy randomization in the reactions of F atoms at the carboxyl sites of CH3COOH and CF3COOH

The HF and DF vibrational distributions for the hydrogen abstraction reactions between F atoms and CH₃COOD, CD₃COOH, CF₃COOD and CF₃COO have been measured by arrested relaxation infrared chemiluminescence. Phase space calculations have been carried out which accurately reproduce the dis observed for the reactions at the carboxyl site in each case. The calculations suggest that the energy is not completely randomised during the acetic a whereas the trifluoroacetic acid reactions show ergodic behaviour.     

Structural features of disubstituted polyacetylenes with bulky substituents at double bonds

The structural features of polyacetylenes carrying two substituents at double bonds with the general formula [-C(CH₃)=CR-] _n , where R = Si(CH₃)₃, -Ge(CH₃)₃, or CH(CH₃)₂, are studied. It is shown that the experimental IR and Raman spectra of the polymers and the theoretically calculated vibrational spectra for the model polymers consisting of three units coincide well with experimental data. All bands in the IR spectra are interpreted. The potential curves of internal rotation are calculated and constructed; high values of rotation barriers indicate a high rigidity of chains for all polymers of interest. The orthogonal arrangement of neighboring monomer units and, as a result, the absence of electron-density conjugation over the polymer chain are revealed. Charges on atoms and electron density on bonds of the monomer unit obtained from theoretical calculations indicate the presence of strong polarization of all bonds, including the -C=C- bond. This effect causes a shift in the frequencies of stretching vibrations due to double bonds in the IR spectra of polyacetylenes with Si- and Ge-containing side substituents toward the longwave region. For polyacetylene with hydrocarbon side substituents -CH(CH₃)₂, such polarization is absent.     

An ONIOM and DFT study of water and ammonia adsorption on anatase TiO2 (001) cluster

Density functional theory (DFT) calculations at ONIOM DFT B3LYP/ 6‐31G**‐MD/UFF level are employed to study molecular and dissociative water and ammonia adsorption on anatase TiO₂ (001) surface represented by partially relaxed Ti₂₀O₃₅ ONIOM cluster. DFT calculations indicate that water molecule is dissociated on anatase TiO₂ (001) surface by a nonactivated process with an exothermic relative energy difference of 58.12 kcal/mol. Dissociation of ammonia molecule on the same surface is energetically more favorable than molecular adsorption of ammonia (?37.17 kcal/mol vs. ?23.28 kcal/mol). The vibration frequency values also are computed for the optimized geometries of adsorbed water and ammonia molecules on anatase TiO₂ (001) surface. The computed adsorption energy and vibration frequency values are comparable with the values reported in the literature. Finally, several thermodynamical properties (ΔH°, ΔS°, and ΔG°) are calculated for temperatures corresponding to the experimental studies. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

An ONIOM and DFT study of water adsorption on rutile TiO2 (110) cluster

Density functional theory (DFT) calculations performed at ONIOM DFT B3LYP/6‐31G**‐MD/UFF level are employed to study molecular and dissociative water adsorption on rutile TiO₂ (110) surface represented by partially relaxed Ti₂₅O₃₇ ONIOM cluster. DFT calculations indicate that dissociative water adsorption is not favorable because of high activation barrier (23.2 kcal/mol). The adsorption energy and vibration frequency of both molecularly and dissociatively adsorbed water molecule on rutile TiO₂ (110) surface compare well with the values reported in the literature. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Methanol oxidation on the PtPd(111) alloy surface: A density functional theory study

The mechanisms of methanol (CH₃OH) oxidation on the PtPd(111) alloy surface were systematically investigated by using density functional theory calculations. The energies of all the involved species were analyzed. The results indicated that with the removal of H atoms from adsorbates on PtPd(111) surface, the adsorption energies of (i) CH₃OH, CH₂OH, CHOH, and COH increased linearly, while those of (ii) CH₃OH, CH₃O, CH₂O, CHO, and CO exhibited odd‐even oscillation. On PtPd(111) surface, CH₃OH underwent the preferred initial C H bond scission followed by successive dehydrogenation and then CHO oxidation, that is, CH₃OH → CH₂OH → CHOH → CHO → CHOOH → COOH → CO₂. Importantly, the rate‐determining step of CH₃OH oxidation was found to switch from CO → CO₂ on Pt(111) to COOH → CO₂ + H on PtPd(111) with a lower energy barrier of 0.96 eV. Moreover, water also decomposed into OH more easily on PtPd(111) than on Pt(111). The calculated results indicate that alloying Pt with Pd could efficiently improve its catalytic performance for CH₃OH oxidation through altering the primary pathways from the CO path on pure Pt to the non‐CO path on PtPd(111).     

Reaction pathways of carboxylic acids over TiO<Subscript>2</Subscript> single crystal surfaces: diketene formation from bromo-acetic acid

This work presents the first investigation of a halo-carboxylic acid (Br-CH2COOH) over the surface of an oxide single crystal (the {011}-faceted TiO₂(001) single crystal). A very rich chemistry is observed. This is broadly divided into three categories: elimination of HBr to make ketene, dimerisation of two molecules of ketene to 4-methyl-2-oxetanone and 1,3-cyclobutanedione, and further reaction of the latter to a mass spectrometer m/e 70 signal attributed to crotonaldehyde (formed by ring opening). Temperature programmed desorption (TPD) and Scanning Kinetic Spectroscopy (SKS) gave complementary results with SKS opening a simple way for investigating surface chemical reactions in UHV conditions with high surface coverage at still high temperatures. A successful modeling of SKS data was conducted providing the activation energies (E _a) for ketene desorption, with a reaction order n close to 1, for both CH₃COOH (E _a = 21.3 kcal/mol) and BrCH₂COOH (E _a = 17.2 kcal/mol). In order to further understand the surface reaction of BrCH₂COOH semi-empirical PM3 computation of its adsorption and reaction on a Ti₈O₂₉H₂₆ cluster representing the (011) TiO₂ surface was conducted and compared to that of CH₃COOH on the same cluster. Dissociative adsorptions of both the O-H and C-Br bonds are more stable than the non-dissociative adsorption modes. The di-coordinated species, TiOC(O)CH₂O_s, formed by the simultaneous dissociation of both C-Br and O-H bonds of BrCH₂COOH appears the most plausible surface intermediate for the observed carbon coupling reactions.     

用密度泛函理论研究一种新型有机硅化合物异构体的振动光谱

在B3LYP/6-31＋G(d)的水平上, 对两种含有手性Si原子的新型有机硅单体Si₂(CH₃)₂H₂N₂(C₂H₅)₄和Si₄(CH₃)₄H₄N₂(C₆H₅)₂的几种异构体进行了研究, 在全参量几何构型优化的基础上, 进行了简谐振动频率计算, 同时对所研究的体系进行了热力学性质和低能激发态的含时密度泛函理论(TDDFT)计算. 理论计算表明, 构象异构体之间的红外光谱差异不大, 热力学和低能激发态性质也相似; 顺/反结构相似的异构体之间红外光谱差异不大, 但热力学和低能激发态性质却呈现差异; 旋光异构体或顺/反结构相差较大的异构体之间, 红外光谱和热力学及低能激发态性质有明显的差异. 从理论上解释了实验红外光谱中Si—H振动峰的裂分是由异构体的存在所致, 并找到裂分峰所对应的异构结构. Si—H键振动频率与其键长相关.     

Methanol Adsorption on TiO2 Film Studied by Sum Frequency Generation Vibrational Spectroscopy (cited:2)

A broadband infrared surface sum frequency generation vibrational spectroscopy (SFG-VS) and an in situ UV excitation setup devoted to studying surface photocatalysis have been constructed. With a home-made compact high vacuum cell, organic contaminants on TiO₂ thin lm surface prepared by RF magnetron sputtering were in situ removed under 266 nm irradiation in 10 kPa O₂ atmosphere. We obtained the methanol spectrum in the CH₃ stretching vibration region on TiO₂ surface with changing the methanol pressure at room temperature. Features of both molecular and dissociative methanol, methoxy, adsorbed on this surface were resolved. The CH₃ symmetric stretching vibration frequency and Fermi resonance of molecular methanol is red-shifted by about 6?8 cm^-1 from low to high coverage. Moreover, the recombination of dissociative methanol and H on surfaces in vacuum was also observed. Our results suggest two equilibria exist: between molecular methanol in the gas phase and that on surfaces, and between molecular methanol and dissociative methanol on surfaces.     

Synthesis, crystal structure and properties of a charge-transfer compound [(CH3)3CNH3]3[PMo12O40] · 2H2O

A charge-transfer compound [(CH₃)₃CNH₃]₃[PMo₁₂O₄₀] · 2H₂O was synthesized and characterized by IR, UV, ESR, diffusion reflectance electronic spectrum, cyclic voltammogram and X-ray crystallography. Oxygen atoms of the polyoxometalate anion, N atoms of organic substrates (CH₃)₃CNH₂ and O atoms of water molecules are involved in hydrogen bonding. The solid reflectance electronic spectra and IR data indicate the presence of interaction between the [PMo₁₂O₄₀]³⁻ and the organic substrates in the solid state. Photosensitivity to ultraviolet light was assessed for the compound, showing that charge-transfer resulted from oxidation of the organic substrates and the reduction of the heteropolyanion.     

A DFT study of acetonitrile adsorption and decomposition on the TiO2 (110) surface

The adsorption and decomposition of acetonitrile on the TiO₂ (110) surface have been investigated with first principles calculations. Our results reveal that both C?N and C? C bonds of acetonitrile become weakened after adsorption. Acetonitrile behaves as an electron donor, and electrons transfer from acetonitrile to substrate is obvious. The reaction mechanism of further decomposition of acetonitrile on TiO₂ (110) surface is also investigated, and the result shows that acetonitrile can decompose into CH₃ and CN fragments and form OCH₃ and NCO groups on the TiO₂ (110) surface, which consists with the experimental results. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Intermediate products and reductive reaction pathways in the TiO2 photocatalytic degradation of 1,1,1-trichloroethane in water

1,1,1-Trichloroethane (TCA) has been chosen for the study of the reducing versus oxidizing steps of carbon, involved in the degradation, in UV-irradiated TiO₂ aqueous suspensions, of chlorinated alkanes containing two C atoms. At wavelengths > 290 nm, TCA disappearance rate was largely increased in the presence of TiO₂. The corresponding apparent first-order rate constant was lower by a factor of only ca. 1.2 than that of nitrobenzene under the same conditions. Within experimental accuracy, the rate of release of Cl ions was equivalent to the TCA disappearance rate, which illustrated the dechlorination efficiency of TiO₂, photocatalysis. Indeed, monochloroacetic acid and, at very low concentrations, monochloroacetaldehyde were the only chlorinated intermediate products detected. Analyses by HPLC of aldehydes (2,4-DNPH derivatization) and carboxylic acids allowed the quantification of ten intermediate products containing these functionalities. Glycolic acid (HO−CH₂−COOH) was the product that reached the highest concentration. From the practical viewpoint, it is important to emphasize that all the organic intermediate products were progressively oxidized. From the fundamental viewpoint, a discussion on the nature and formation pathways of the intermediate products brings evidence of the coexistence of reduction and oxidation steps involving the organic material; detection of cis-butenedioic acid, however at very low concentrations, indicated the existence of coupling radical reactions.     

Charge state of metal atoms on oxide supports: a systematic study based on simulated infrared spectroscopy and density functional theory

A long standing question in the study of supported clusters of metal atoms in the properties of metal–oxide interfaces is the extent of metal–oxide charge transfer. However, the determination of this charge transfer is far from straight forward and a combination of different methods (both experimental and theoretical) is required. In this paper, we systematically study the charging of some adsorbed transition metal atoms on two widely used metal oxides surfaces [α-Al₂O₃ (0001) and rutile TiO₂ (110)]. Two procedures are combined to this end: the computed vibrational shift of the CO molecule, that is used as a probe, and the calculation of the atoms charges from a Bader analysis of the electron density of the systems under study. At difference from previous studies that directly compared the vibrational vawenumber of adsorbed CO with that of the gas phase molecule, we have validated the procedure by comparison of the computed CO stretching wavenumbers in isolated monocarbonyls (MCO) and their singly charged ions with experimental data for these species in rare gas matrices. It is found that the computational results correctly reproduce the experimental trend for the observed shift on the CO stretching mode but that care must be taken for negatively charged complexes as in this case there is a significative difference between the total charge of the MCO complex and the charge of the M atom. For the supported adatoms, our results show that while Cu and Ag atoms show a partial charge transfer to the Al₂O₃ surface, this is not the case for Au adatoms, that are basically neutral on the most stable adsorption site. Pd and Pt adatoms also show a significative amount of charge transfer to this surface. On the TiO₂ surface our results allow an interpretation of previous contradictory data by showing that the adsorption of the probe molecule may repolarize the Au adatoms, that are basically neutral when isolated, and show the presence of highly charged Au^δ+–CO complexes. The other two coinage metal atoms are found to significatively reduce the TiO₂ surface. The combined use of the shift on the vibrational frequency of the CO molecule and the computation of the Bader charges shows to be an useful tool for the study the charge state of adsorbed transition metal atoms and allow to rationalize the information coming from complementary tools.     

Ab initio calculations of isotropic hyperfine coupling constants in β-ketoenolyl radicals

Ab initio unrestricted Hartree–Fock (UHF ), unrestricted second-order Møller–Plesset (UMP 2) perturbation, unrestricted coupled cluster (UCCD ), and unrestricted quadratic configuration interaction (UQCISD ) calculations have been performed on the organic radicals CH₃, CH₃CH₂, CH₂CHCH₂, CH₃CHCOO^?, HCOCHCOH, CH₃COCHCOH, CH₃COCHCOCH₃, and CH₃COC(CH₃)COCH₃, using double-zeta and split-valence-plus-polarization basis sets. These radicals are derived from common organic ligands and have been observed in recent experimental work on tris(β-ketoenolato)cobalt(III) complexes. Their geometry has been optimized at the UHF level using the two mentioned basis sets. From these calcuations, values for the isotropic hyperfine coupling constants at the hydrogen atoms are predicted and compared with the experimental results. The usefulness of semiempirical extrapolations based on limited basis sets and treatment of electron correlation effects is carefully analyzed in the examples considered. © 1994 John Wiley & Sons, Inc.     

Theoretical study of CO and H2O interaction on (110) and (101) Zirconia surfaces

Theoretical calculations of CO and H₂O adsorption on (110) and (101) tetragonal Zirconia surfaces were carried out using ONIOM2 methodology. The calculations showed that the adsorption processes are exothermic reactions with energy values of −28.4 kcal/mol for H₂O on the (110) surface, −51.0 kcal/mol for H₂O on the (101) surface, −21.7 kcal/mol for CO on (110) surface and −23.4 kcal/mol for CO on (101) surface. Analysis of the results suggest that different kinds of basic sites can be found on the (110) and (101) surfaces. In both (110) and (101) surfaces, CO adsorption is on bridged (bonded to two Zr atoms on the (110) surface, bonded to one Zr and O atoms on the (101) surface). The calculations showed that ONIOM can be a powerful tool to study structural and thermodynamics properties of solid surfaces.     

Theoretical study of the force field and vibrational assignments of acetamide and deuterated analogues

The complete harmonic force constants of acetamide have been evaluated by ab initio calculations at the Hartree-Fock level with the 4–31G(d) basis set. The force field was scaled to compensate for the systematic overestimations of the Hartree-Fock-level force constants by empirical factors using the matrix isolation IR spectra of CH₃CONH₂ and CD₃CONH₂. A normal coordinate treatment has been carried out with the scaled force field to analyze the vibrational spectra of CH₃CONH₂. A normal coordinate treatment has been carried out with the scaled force field to analyze the vibrational spectra of CH₃COND₂, cis-CH₃CONHD and trans-CH₃CONHD. The effect of cis/trans isomerism of CH₃CONHD on the fundamental bands was well reproduced by the calculations. The fundamental vibrations were also predicted for CD₃COND₂, cis-CD₃CONHD and trans-CD₃CONHD.     

Vibrational Structure of Methacrylates Europium(Iii) and Lanthanum(Iii): Dft and Ir Spectroscopy Study

DFT-D3/PBE0 and IR spectroscopy are employed to study the vibrational structure of europium(III) and lanthanum(III) methacrylates Ln(Macr)₃ (Ln = Eu, La; Macr is the methacrylate anion, CH₂CH(CH₃)COO^–). The calculated geometric and vibrational characteristics are consistent with the experimental data. By means of the calculation of the Eu₂(Macr)₆·(H₂O)₄ complex the experimental IR spectrum is interpreted. The effect of isomorphic lanthanum substitution for the europium ion in the Eu₂(Macr)₆·(H₂O)₄ complex is studied theoretically. A mechanism is proposed for the effect of the vibrational structure on the optical properties (at the isomorphic replacement of the europium ion and temperature elevation).     

Application of π‐Extended Ferrocene with Varied Anchoring Groups as Photosensitizers in TiO2‐Based Dye‐Sensitized Solar Cells (DSSCs)

Two new compounds, FcCHNC₆H₄COOH ( 1 ) and FcCHNCH₂CH₂OH ( 2 ) (Fc=C₅H₄FeC₅H₅), have been synthesized and characterized by elemental analyses, IR and ¹H NMR spectroscopy, and ESI‐MS. Attempt has been made to explain their quasi‐reversible redox behavior evidenced by cyclic voltammetry using density functional theory (DFT) calculations. Light‐harvesting properties of both the compounds and also the starting material, FcCHO ( 3 ), have been studied using these compounds as photosensitizers in TiO₂‐based dye‐sensitized solar cells having either a propylene carbonate‐based electrolyte or ionic liquid electrolyte, namely, 1‐propyl‐3‐methyl imidazolium iodide (PMII). Long‐term stability of the photocurrent output of the cell using compound 1 as photosensitizer has been monitored periodically over 1400 h.     

Role of Reduced Defects for Coupling Reactions of Acetaldehyde on Anatase TiO2(001)-(1×4) Surface

The chemistry of acetaldehyde (CH₃CHO) adsorbed on the anatase TiO₂(001)-(1×4) surface has been investigated by temperature-programmed desorption (TPD) method. Our experimental results provide the direct evidence that the perfect lattice sites on the anatase TiO₂(001)-(1×4) surface are quite inert for the reaction of CH₃CHO, but the reduced defect sites on the surface are active for the thermally driven reductive carbon-carbon coupling reactions of CH₃CHO to produce 2-butanone and butene. We propose that the coupling reactions of CH₃CHO on the anatase TiO₂(001)-(1×4) surface should undergo through the adsorption of paired CH3CHO molecules at the reduced defect sites, since the existing reduced Ti pairs provide the suitable adsorption sites.