Equilibrium crystal shapes: towards absolute energies

An increasing number of investigations are focussing on the equilibrium shapes of 2D and 3D crystallites that are being imaged at high resolution by scanning electron probes. Features, such as facets and vicinal surfaces on 3D equilibrium crystal shapes (ECS), are of particular interest since they offer a route towards the evaluation of relative step-formation and step-interaction energies. It is shown that a measurement of the temperature dependence of the ECS, in particular of facet shapes and sizes, can be used to extract absolute step and surface free energies. This novel approach appears to be capable of providing surface free energies over a sufficiently large range of temperatures, such that an extrapolation to even 0 K can be done. Thus, a meaningful comparison of experimental and theoretical surface energies comes into view.     

Self-assembled parallel mesoscopic Pb-wires on Au-modified Si(5 3 3) substrates

Arrays of extremely long and perfectly parallel mesoscopic Pb-wires are formed and studied in UHV conditions. Au-modified Si(5 3 3) substrate modified by deposition of sub-monolayer amount of Au are used as templates. A uniform distribution of monoatomic steps and terraces on well-oriented Si(5 3 3) is induced by formation of Au-chains running along step edges. Real-time surface imaging with LEEM shows that the wires growing on substrates held at temperatures close to the room temperature are all aligned parallel to azimuth, along the step edges. After nucleation of elongated islands, the 1 ML thick wetting layer remains on the vicinal Si surface. RHEED and low-temperature STM experiments show that the wires have triangular cross-section, limited by (1 1 1) and (1 0 0) facets of Pb. The width of the wires is 60 nm, whereas their length is up to 8 μm. The observed growth anisotropy leading to the formation of mesoscopic wires is attributed to enhanced one-dimensional diffusion along the parallel grooves and trenches that form vicinal surfaces. An additional factor, contributing to the anisotropic growth, is probably the anisotropic strain, due to the large misfit between Pb and Si lattices.     

Advanced AC calorimetry of polycaprolactone in melting region

The new capabilities of AC calorimetry, when working at frequencies above the classical limit were demonstrated. The appropriate frequency range of classical AC calorimetry was substantially enlarged. It was shown that the advanced AC calorimetry can be applied for studying dynamic heat capacity of polymers in the frequency range 0.1–1 Hz. Thus, the processes with characteristic time as short as ca. 5 s was registered. The advanced AC technique was applied for investigation of the melting kinetics in polycaprolactone. It was found that melting in polycaprolactone is related to an activated process. The activation of the melting process after a step heating is described by a stretched exponent and the decay of the melting by only one exponent at short times. The dependencies of the exponent on temperature and thermal treatment were investigated at frequencies in the range 0.1–1Hz and modulation amplitudes 0.005–0.2 K.     

Silica gel ethyleneimine and its adsorption capacity for divalent Pb, Cd, and Hg

Activated silica gel was directly modified with a cyclic molecule, ethyleneimine, yielding a surface with various nitrogen basic centers, ≡Sil–O(CH₂CH₂NH)_nCH₂CH₂NH₂. Infrared spectroscopy, ¹³C NMR, thermal, and elemental analyses confirmed the covalent attachment of the organic species onto the silica matrix. The purpose of this paper is to describe the interaction involving the grafted species on silica surface with the divalent heavy cations, Pb(II), Cd(II), and Hg(II), from aqueous solutions at room temperature. The process of metal extraction was followed by the batch method and the order of the maximum extraction capacities found was: 1.27 ± 0.04, 1.02 ± 0.02, and 0.98 ± 0.01 mmol g⁻¹ for Pb(II), Cd(II), and Hg(II) chlorides, respectively. These interactions were followed by calorimetric titration. The enthalpies of these processes are: −3.05 ± 0.02, −1.09 ± 0.01, and −9.88 ± 0.03 kJ mol⁻¹ for Pb(II), Cd(II), and Hg(II), respectively. The standard molar Gibbs free energies are in agreement with the spontaneity of the proposed reactions between cation and basic center.     

Effects and structures of the O/Cu surfactant layer in O-mediated film growth of Cu on Ru(0 0 0 1)

The O-mediated Cu-film growth on O-precovered Ru(0 0 0 1) is investigated by means of scanning tunneling microscopy for growth temperatures between 300 and 600 K. Cu-films on clean Ru(0 0 0 1) grow in a multilayer mode. For O precoverages (Θ) between 0.2 ML (monolayer) and the saturation coverage (Θ=0.5 ML), a layer-by-layer growth is observed at growth temperatures between 350 and 450 K. On Cu-islands, an O/Cu surfactant layer is formed, which floats on-top of the growing film and induces the layerwise Cu-film growth. The surface coverage of the O/Cu surfactant layer linearly rises with the O precoverage up to Θ≈0.4 ML, where it completely covers the surface. Two different types of the surfactant layer are identified, inducing different surfactant mechanisms. For Θ=0.1–0.4 ML, the O/Cu surfactant structure (A-type) displays some local order and induces inhomogeneous nucleation at the misfit-induced relaxation structure of the Cu-film. The layer-wise growth is explained by the concept of two mobilities, implying a large attempt frequency for adatom jumps over the interlayer diffusion barrier at the steps. For Θ = 0.4–0.5 ML, a disordered O/Cu surfactant layer is established (B-type), inducing homogeneous nucleation. The layer-wise Cu-film growth is attributed to a reduction of the effective interlayer diffusion barrier. Cu-film growth at 400 K on the ordered (3×2√3)O/Cu structure formed at temperatures around 520 K yields the conclusion that the O/Cu surfactant structures are composed of randomly arranged O–Cu–O strings and disrupted “Cu₂O(1 1 1)” fragments.     

Syntheses, crystal structures and electronic properties of a series of copper(II) complexes with 3,5-halogen-substituted Schiff base ligands and their solutions

We have systematically investigated the structural features, electronic properties, thermally-induced structural phase transitions and absorption spectra depending on the solvent for ten Cu(II) complexes with 3,5-halogen-substituted Schiff base ligands. Structural characterization of two new complexes, bis(N-R-1-phenylethyl- and N-R,S-2-butyl-5-bromosalicydenaminato-κ²N,O)copper(II), reveals that they afford a compressed tetrahedral trans-[CuN₂O₂] coordination geometry with trans-N–Cu–N = 159.4(2)° and trans-O–Cu–O = 151.7(3)° for the 1-phenylethyl complex and trans-N–Cu–N = 157.9(3)° and trans-O–Cu–O = 151.0(3)° for the 2-butyl one. All the complexes exhibit a structural phase transition by heating in the solid state regardless of their structures at room temperature. The absorption spectra of a series of ten complexes exhibit a slight shift of the d–d band at 16 000–20 000 cm⁻¹ and remarkable shift of the π–π* band at 24 000–28 000 cm⁻¹, which suggests that the dipole moment of the solvents presumably affects the conformation of the π-conjugated moieties of the ligands rather than the coordination environment. We have also attempted ‘photochromic solute-induced solvatochromism’ by a system of bis(N-R-1-phenylethyl-3,5-dichlorosalicydenaminato-κ²N,O)copper(II) and photochromic 4-hydroxyazobenzene in chloroform solution. We successfully observed a change of the d–d and π–π* bands of the complex in the absorption spectra caused by cis–trans photoisomerization of 4-hydroxyazobenzene.     

Quantum size effects in the low temperature layer-by-layer growth of Pb on Ge(0 0 1)

The electronic properties of thin metallic films deviate from the corresponding bulk ones when the film thickness is comparable with the wavelength of the electrons at the Fermi level. This phenomenon, referred to as quantum size effect (QSE), is also expected to affect the film morphology and structure leading to the “electronic growth” of metals on semiconductors. Such effect may be observed when metals are grown on substrates held at low temperature and are manifested through the occurrence of “magical” thickness islands or critical thickness for layer-by-layer growth. In particular, layer-by-layer growth of Pb(1 1 1) films has been reported for deposition on Ge(0 0 1) below 130 K. An extremely flat morphology is preserved throughout deposition from four up to a dozen of monolayers. These flat films are shown to be metastable and to reorganize into large clusters uncovering the first Pb layer pseudomorphic to the underlying Ge(0 0 1) substrate already at room temperature. Indications of QSE induced structural variations of the growing films have been reported for Pb growth on both Si(1 1 1) and Ge(0 0 1). In the latter case, the apparent height of the Pb(1 1 1) monatomic step was shown to change in an oscillatory fashion by He atom scattering (HAS) during layer-by-layer growth at low temperature. The extent of the structural QSE has been obtained by a comparison of the HAS data with X-ray diffraction (XRD) and reflectivity experiments. Whereas step height variations as large as 20% have been measured by HAS reflectivity, the displacement of the atomic planes from their bulk position, as measured by XRD, has been found to mainly affect the topmost Pb layer, but with a lower extent, i.e. the QSE observed by HAS are mainly due to a perpendicular displacement of the topmost layer charge density. The effect of the variable surface relaxation on the surface vibration has been studied from the acoustic dispersion of the low energy phonons, as measured by inelastic HAS.     

Selective IR-induced isomerization of 1,2-dichloropropane isolated in xenon matrix

The conformations of monomeric 1,2-dichloropropane isolated in low temperature xenon matrix were characterized experimentally using FTIR spectroscopy. The interpretation of the experimental spectra was aided by ab initio MP2/6-311++G(3df,3pd) calculations. Relative energies of three structures, differing by the orientation of the Cl−C−C−Cl dihedral angle, fall within 0–6 kJ mol⁻¹ range. The spectral signatures of all three conformers were identified experimentally. Infrared irradiation of the matrix isolated compound resulted in selective conversion of the most stable Trans conformer into the higher energy Gauche+ rotamer, while the Gauche− conformer remained unaffected. This result was interpreted in terms of calculated energy barriers and dipole moments.     

Langmuir monolayer properties of the fluorinated-hydrogenated hybrid amphiphiles with dipalmitoylphosphatidylcholine (DPPC)

Surface pressure–area (π–A), surface potential–area (ΔV–A), and dipole moment–area (μ–A) isotherms were obtained for the Langmuir monolayer of two fluorinated-hydrogenated hybrid amphiphiles (sodium phenyl 1-[(4-perfluorohexyl)-phenyl]-1-hexylphosphate (F6PH5PPhNa) and (sodium phenyl 1-[(4-perfluorooctyl)-phenyl]-1-hexylphosphate (F8PH5PPhNa)), DPPC and their two-component systems at the air/water interface. Monolayers spread on 0.02 M Tris buffer solution (pH 7.4) with 0.13 M NaCl at 298.2 K were investigated by the Wilhelmy method, ionizing electrode method and fluorescence microscopy. Moreover, the miscibility of two components was examined by plotting the variation of the molecular area and the surface potential as a function of the molar fraction for the fluorinated-hydrogenated hybrid amphiphiles on the basis of the additivity rule. The miscibility of the monlayers was also examined by construction of two-dimensional phase diagrams. Furthermore, assuming the regular surface mixture, the Joos equation for analysis of the collapse pressure of two-component monolayers allowed calculation of the interaction parameter (ξ) and the interaction energy (−Δ) between the fluorinated-hydrogenated hybrid amphiphiles and DPPC. The observations by a fluorescence microscopy also supported our interpretation as for the miscibility in the monolayer state. Comparing the monolayer behavior between the two binary systems, no remarkable difference was found among various aspects. Among the two combinations, the mole fraction dependence in monlayer properties was commonly classified into two ranges: 0 ≤ X ≤ 0.3 and 0.3 < X ≤ 1. Dependence of the chain length of fluorinated part was reflected for the molecular packing and surface potential.     

Spectroscopy of C–H stretching vibrations of gas-phase cyclohexene

The fundamental and overtone spectra of the C–H stretching of cyclohexene in the gas phase have been measured using FTIR spectroscopy in the range 2800–11 500 cm⁻¹ (Δv=1–4) and intracavity dye laser spectrometry in the range 12 900–17 500 cm⁻¹ (Δv=4–7). Up to Δv=6, the spectra show disturbed structure. The transitions observed are mainly interpreted on the basis of a comparative study with the previous experimental and theoretical work relative to 3,3,6,6-d₄-cyclohexene. Ab initio calculations of molecular geometries and fundamental vibrational frequencies have also been performed in a molecule-fixed cartesian coordinates to calculate the first derivative of the dipole moment function and of the polarisability tensor in order to reproduce the fundamental infrared and Raman spectra. In the overtone spectra, possibility of Fermi resonances between the methylenic C–H bond stretchings and combination states involving other low-frequency modes is qualitatively discussed.     

Theoretical study on the structure and UV–visible spectrum of pyridine–chloranil charge-transfer complex

The ground-state structure of the charge-transfer complex formed by pyridine (Py) as electron donor and chloranil (CA) as acceptor has been studied by full geometry optimization at the MP2 and DFT levels of theory. Binding energies were calculated and counterpoise corrections were used to correct the BSSE. Both MP2 and DFT indicate that the pyridine binds with chloranil to form an inclined T-shape structure, with the pyridine plane perpendicular to the chloranil. The CP and ZPE corrected binding energies were calculated to be 14.21 kJ/mol by PBEPBE/6-31G(d) and 23.21 kJ/mol by MP2/6-31G(d). The charge distribution of the ground state Py–CA complex was evaluated with the natural population analysis, showing a net charge transfer from Py to CA. Analysis of the frontier molecular orbitals reveals a σ–π interaction between CA and Py, and the binding is reinforced by the attraction of the O₇ atom of CA with the H₂₃ atom of Py. TD-DFT calculations have been performed to analyze the UV–visible spectrum of Py–CA complex, revealing both the charge transfer transitions and the weak symmetry-relieved chloranil π–π^* transition in the UV–visible region.     

Kinetic modeling of promotion and inhibition of temperature on photocatalytic degradation of benzene vapor

This study investigated the effects of temperature, humidity, and benzene concentration on the photocatalytic oxidation of benzene vapor over titanium dioxide. An annular packed-bed photocatalytic reactor was employed to determine the intrinsic oxidation rates for the photocatalysis of benzene. Degussa P-25 TiO₂ was used as the photocatalyst and a 15 W near-UV lamp (350 nm) was used as the light source. The experiments were conducted at influent benzene concentrations of 250–450 ppmv, water vapor concentrations of 13,500–27,500 ppmv, and reaction temperatures ranging from 100 to 200 °C. Benzene oxidation rates increased with temperature below 160–180 °C, but decreased with temperature above 160–180 °C. Raising the reaction temperature increased the chemical reaction rates but reduced the reactant adsorption rate on TiO₂ surfaces. The overall reaction rate increased with temperature, indicating that the reduction of reactant adsorption rate did not affect the overall reaction, and thus the chemical reaction was the rate-limiting step. As the chemical reaction rate gradually exceeds the reactant adsorption rate with temperature, the rate-limiting step was shifted from the chemical reaction to the reactant adsorption. Additionally, the competitive adsorption between benzene and water for the active sites on TiO₂ resulted in the promotion and inhibition of reaction rate by humidity. This study developed a modified bimolecular Langmuir–Hinshelwood kinetic model to simulate the temperature and humidity related promotion and inhibition of the photocatalysis of benzene. The correlation developed here was used as a basis for determining the apparent activation energy of 0.76 kcal/mol and adsorption enthalpies of benzene and water of −20.1 and −13.7 kcal/mol.     

Direct dynamic study on the hydrogen abstraction reaction C2(Πu)+H2 → C2H+H

The ab initio direct dynamics method at the G2//UQCISD/6-311 + G(d,p) level is employed to study the hydrogen abstraction reaction C₂(³Π_u)+H₂ → C₂H+H over a wide temperature range 100–4650 K. The barrier heights obtained for the forward and reverse reactions are 7.78 and 17.53 kcal/mol, respectively. Comparing with one recent experiment, the calculated forward rate constants over the temperature range 2580–4650 K are about 4.4–13.5 times greater and show a steeper temperature-dependent effect. This indicates that further experimental investigation on this simple radical reaction may still be desired. Finally, G2//UQCISD/6-311 + G(2df,2p) calculations are performed to test the reliability of the G2//UQCISD/6-311 + G(d,p) results.     

Raman scattering study of highly fluorinated graphite

Raman spectra of highly fluorinated C_xF samples (1<x<2) prepared at room temperature and 515°C were measured. C_xF samples prepared at room temperature exhibited two Raman bands at 1593–1583 and 1555–1542 cm⁻¹. Graphite samples fluorinated at 515°C for 1 and 2 min also gave similar bands at 1581–1580 and 1550–1538 cm⁻¹. However, graphite samples fluorinated from 15 min to 10 h at 515°C no longer showed such spectra. The Raman peaks shifted to lower frequencies with increasing fluorine concentration in C_xF. This trend is due to the weakening of the C---C bonds of the graphene layers. Observation of both kinds of Raman bands suggests the coexistence of two highly fluorinated phases, C₂F and C₁F, in the samples. The process of formation of graphite fluoride is discussed on the basis of the Raman spectra of C_xF samples obtained at 515°C.     

Heat capacity of copper hydride

The heat capacity of copper hydride has been measured in the temperature range 2–60 and 60–250 K using two adiabatic calorimeters. Special procedure for the purification of CuH has been applied and a careful analysis of sample contamination has been performed. The experimental results have been extrapolated up to 300 K due to instability of the copper hydride at room temperature. From the temperature dependence of heat capacity the values of entropy S°(T), thermal part of enthalpy H°(T)−H°(0) and Gibbs function [−(G°(T)−H°(0))] have been calculated assuming S°(0)=0. The standard absolute entropy, standard entropy of formation from the elements and enthalpy of decomposition of copper hydride from the elements have been calculated and found to be 130.8 J K⁻¹ mol⁻¹ (H₂), −85.1 J K⁻¹ mol⁻¹ (H₂), −55.1 kJ mol⁻¹ (H₂), respectively. These new results gave the possibility of discussion on thermodynamic properties of copper hydride. Debye temperature has been for the first time determined experimentally.     

Extraction of Pb(II), Cd(II), and Hg(II) from aqueous solution by nitrogen and thiol functionality grafted to silica gel measured by calorimetry

The reaction of ethylene sulfide with 3-aminopropyltrimethoxysilane gave a new silylating agent, which was anchored onto a silica surface via the sol–gel procedure. This surface displayed a chelating moiety containing nitrogen and two sulfur basic centers potentially capable of extracting cations from aqueous solutions. The process of metal extraction was followed by a batch method, and fitted to a modified Langmuir equation. The maximum adsorption capacities found were: 2.06 ± 0.01, 3.72 ± 0.02, and 5.14 ± 0.02 mmol g⁻¹ for Pb(II), Cd(II), and Hg(II), respectively. The enthalpies of bending are: −1.16 ± 0.04, −3.60 ± 0.10, and −8.94 ± 0.03 kJ mol⁻¹ for Cd(II), Pb(II), and Hg(II), respectively. The Gibbs free energies of binding agree with the spontaneity of the proposed reactions between cations and basic centers.     

Pressurized solvent extraction and monolithic column-HPLC/DAD analysis of anthocyanins in red cabbage

The aim of this work was to develop a fast method for extraction and analysis of anthocyanins in red cabbage. Pressurized hot water containing 5% of ethanol was used as an extremely efficient extraction solvent. HPLC/DAD with a monolithic column was used to accomplish a fast analysis—24 anthocyanin peaks within 18 min. Statistical design was used to optimize the studied extraction parameters: temperature (80–120 °C); sample amount (1–3 g); extraction time (6–11 min); concentration of formic acid in the extraction solvent (0–5 vol.%). The best extraction conditions for a majority of the anthocyanin peaks were 2.5 g of sample, 99 °C (at 50 bar), 7 min of extraction and a solvent composition of water/ethanol/formic acid (94/5/1, v/v/v).     

Temperature study of Raman, FT-IR and photoluminescence spectra of ZnPc thin layers on Si substrate

The temperature study of zinc phthalocyanine (ZnPc) thin layers deposited on (0 0 1) Si substrate using Raman, FT-IR absorption and photoluminescence (PL) methods are reported. The Raman scattering spectra of ZnPc layers were investigated in the spectral range 1250–1650 cm⁻¹ and in the temperature range 100–500 K. The changes of spectral parameters such as the band position, integrated intensity and full width at half maximum (FWHM) of selected Raman modes while heating and cooling processes have been determined. The fast decrease of the frequency and the intensity of these modes observed with the increase of the temperature above 420 K, can be probably caused by the change of crystalline form of ZnPc thin layer. The FT-IR measurements have been performed in the temperature range 98–523 K. Our study allowed us to estimate the orientation of the molecular plane similar to these of CuPc thin films deposited on Si substrate. The Raman spectra have been compared with FT-IR spectra of ZnPc molecules in KBr pellets and thin layers of ZnPc on (0 0 1) Si substrate. The PL spectra of ZnPc layers were measured in the spectral range 350–1200 nm and in the temperature range 13–320 K. With increasing temperature from 13 to 175 K we observed the increase of PL bands at 1.76 and 1.85 eV which disappear reaching temperature above 200 K.     

Solvent-mediated tautomerization of purine: single to quadruple proton transfer

We present calculations for the structures and the tautomerization reaction of purine and purine – (H₂O)_n (n=1–3) clusters. We find two pathways (via the carbene and the sp³-type intermediate) for the 9 ↔ 7 tautomerization of bare purine. The barrier heights for the 9 → 3 and 9 → 7 tautomerization of bare purine are calculated to be large (60–70 kcal/mol). Hydrogen bonding with the water molecule(s), however, dramatically lowers the 9 → 3 barrier by the concerted multiple proton transfer mechanism, favoring the formation of the conformer 3(H)- relative to the 7(H)-purine in the microsolvated environment, in contrast to the gas phase or the aqueous solution.     

A comparative study on the nature and strength of O–O, S–S, and Se–Se bond

A computational study on dichalcogenide molecules (R₂X₂; X = O, S, Se; R = H, CH₃, NH₂) has been carried out employing B3LYP and MP2 levels using 6-31+G*, 6-311+G*, 6-311++G**, and PVDZ basis sets. The relative energies have been evaluated at G2MP2 also. The rotational barriers and bond dissociation energies indicate that S–S bond is stronger than Se–Se and O–O bond. NBO analysis at MP2/6-31+G* suggest the presence of partial π character between X–X bond that decreases in the order S–S > Se–Se > O–O. Fuki functions for nucleophilic and electrophilic attack fail to distinguish the reactivity of S and Se. The proton affinities of the O₂H₂, S₂H₂, Se₂H₂ decrease in the order Se > S > O.