Theoretical investigation of intramolecular π-type hydrogen bonding and internal rotation of 2-cyclopropen-1-ol, 2-cyclopropen-1-thiol and 2-cyclopropen-1-amine

ABSTRACT

Theoretical computations utilising both CCSD and MP2 methods and the cc-pVTZ basis set have been carried out to determine the structures of several conformations as well as the internal rotation potential energy functions for 2-cyclopropen-1-ol, 2-cyclopropen-1-thiol and 2-cyclopropen-1-amine. The energies and wavefunctions for these potential functions have also been computed. Each of these molecules has an energy minimum corresponding to a conformation with intramolecular π-type hydrogen bonding. The π bonding stabilisation is about 2.3?kcal/mole for the alcohol, 2.1?kcal/mole for the thiol, and about 2.5?kcal/mole for the amine. The results for the thiol demonstrate a rare example of intramolecular π-type hydrogen bonding. The calculated O–H, S–H, N–H, and C=C stretching frequencies have also been compared for the conformations with and without the π-type hydrogen bonding. The C=C stretching frequency is substantially lower in all cases for the hydrogen bonded conformers.     

Effects of Surface Dipole Lengths on Evaporation of Tiny Water Aggregation

Using molecular dynamics simulation, we compared evaporation behavior of a tiny amount of water molecules adsorbed on solid surfaces with different dipole lengths, including surface dipole lengths of 1 fold, 2 folds, 4 folds, 6 folds and 8 folds of 0.14 nm and different charges from 0.1e to 0.9e. Surfaces with short dipole lengths (1-fold system) can always maintain hydrophobic character and the evaporation speeds are not influenced, whether the surface charges are enhanced or weakened; but when surface dipole lengths get to 8 folds, surfaces become more hydrophilic as the surface charge increases, and the evaporation speeds increase gradually and monotonically. By tuning dipole lengths from 1-fold to 8-fold systems, we confirmed non-monotonic variation of the evaporation flux (first increases, then decreases) in 4 fold system with charges (0.1e-0.7e), reported in our previous paper [S. Wang, et al., J. Phys. Chem. B 116 (2012) 13863], and also show the process from the enhancement of this unexpected non-monotonic variation to its vanishment with surface dipole lengths increasing. Herein, we demonstrated two key factors to influence the evaporation flux of a tiny amount of water molecules adsorbed on solid surfaces: the exposed surficial area of water aggregation from where the water molecules can evaporate directly and the attraction potential from the substrate hindering the evaporation. In addition, more interestingly, we showed extra steric effect of surface dipoles on further increase of evaporation flux for 2-folds, 4-folds, 6-folds and 8-folds systems with charges around larger than 0.7e. (The steric effect is first reported by parts of our authors [C. Wang, et al., Sci. Rep. 2 (2012) 358]). This study presents a complete physical picture of the influence of surface dipole lengths on the evaporation behavior of the adsorbed tiny amount of water.     

Conformational Studies of 1-(2′-Hydroxythiobenzoyl)piperidine and 4-(2′-Hydroxythiobenzoyl)morpholine by High Resolution N.M.R. Spectroscopy

Abstract

The 220 MHz ¹H nmr spectra of the title compounds (1a) and (2a), respectively, at low temperature in CDCl₃ solution are interpreted in terms of two interconverting chair forms with unequal populations (K_e = 1.17, δG° ～70 cals/mole for 1a and K_e = 1.8, δG° ～0.2 kcal/mole for 2a at ?30°C). A strong intramolecular OH…S hydrogen bond in both compounds reduces the number of degrees of freedom of the bulky N-thiobenzoyl substituent, which nearly eclipses the equatorial α-CH₂ hydrogen atoms in both comformations. Steric interactions between the 6′ phenyl proton and the hetero-ring α-CH₂ protons trans to the thiocarbonyl group are different in the two conformations of la and 2a.     

Crystal field surface orbital-bond energy bond order (CFSO-BEBO) calculations of adsorption: II. Carbon monoxide,oxygen and carbon dioxide on platinum (111) and oxygen on nickel (111)

The Crystal Field Surface Orbital-Bond Energy Bond Order (CFSO-BEBO) model of chemisorption is applied to the interaction of carbon monoxide, oxygen and carbon dioxide with a (111) platinum surface; and the interaction of oxygen with a (111) nickel surface. No activation energy for molecular adsorption of carbon monoxide on platinum is predicted; however a large activation energy for dissociative chemisorption is calculated. The molecular state has a binding energy of approximately 28 kcal/mole, and vibrational stretching frequencies of 1935 and 1975 cm^?1 are calculated by combining the CFSO-BEBO model with Badger's Rule. The adsorption of oxygen on (111) platinum and (111) nickel are predicted to be different in the following respects: (1) There is an activation energy of 2.1–4.5 kcal/mole on platinum, whereas adsorption on nickel is unactivated; and (2) The dissociative heat of chemisorption on platinum is 58–68 kcal/mole, whereas on nickel it is substantially larger, 112–116 kcal/mole. The adsorption of carbon dioxide on (111) platinum is predicted to be not only highly activated but also endothermic. All of the calculated results are essentially in quantitative agreement with available experimental data.     

不同形态MEH-PPV的构象及其光学特性

通过对在固溶体、稀溶液、薄膜和纳米孔中MEH—PPV的PL和PLE谱的测量分析,研究不同形态下MEH-PPV分子链的构象及其对电子能带和光学性质的影响。在THF稀溶液中,MEH—PPV分子链基本上皆为分立态;在MEH—PPV薄膜中,分子链基本上皆为聚集态;在MEH-PPV／PS固溶体中,MEH—PPV分子链为聚集态和分立态两构象并存,聚集态的比例随MEH-PPV浓度的增加而升高;在多孔氧化铝模板纳米孔中,MEH—PPV分子链形成链束。分立态、聚集态和链束这三种不同构象的分子链具有不同的电子能带结构和光学性质。     

Adsorption,diffusion and self-diffusion on tungsten surfaces with adsorbed palladium

The influence of a Pd adsorption layer on the surface self-diffusion of tungsten has been measured using a field emitter technique. By adsorption of 1.2 × 10¹⁵ Pd atoms/cm² — measured by high energy ion backscattering — the surface self-diffusion energy decreases from 70 to 54 kcal/mole, and the diffusivity from 0.95 to about 0.2 cm²/s, which corresponds to an increase of the diffusion coefficient by a factor 40 at 1600 K and 80 at 1400 K. Furthermore are determined (1) adsorption lifetimes in adsorption-desorption equilibria, (2) the isosteric adsorption heat (103 kcal/mole), and (3) the coefficient of Pd surface diffusion on W resulting in diffusion energies of 32 kcal/mole around (001) and 17 kcal/mole around (111).     

Infrared studies of single crystals of polycaprolactam

Infrared studies of the α-crystalline form of polycaprolactam (nylon 6) have confirmed the assignment of the 1288 and 1210-cm^?1 bands to a unique fold conformation. The γ-crystalline phase has a band at 1212 cm^?1 which overlaps the 1210-cm^?1 fold band in samples containing both α and γ phases. The 1288-cm^?1 band was, therefore, used to monitor regular fold content. No unique fold bands were detected in the γ form. Irregular folds present in solution-grown crystals regularize to the unique fold conformation upon annealing. Crystals which originally exhibit slight differences in regular folding as a result of different crystallization history have similar amounts of regular folds upon annealing at 220°C. Crystals grown from solutions of very dilute concentrations of polymer have different amounts of regular folding. The annealing behavior of crystals prepared from two different solution concentrations reflect the processes of regularization and long period increase.     

Low temperature sublimation processes from clean cleaved polar surfaces of zinc oxide crystals during first heating

Sublimation of the polar surfaces of ZnO has been studied in ultrahigh vacuum with a quadrupole mass spectrometer and measurements of the emitted ion current. During the first heating cycle the onset of vaporization is detected aready at 380 °C. About one monolayer comes off below the region of reproducible sublimation rates (about 600–900 °C). From the exponential increase in the high temperature range an activation energy is derived: 85 kcal/mole for the Zn surface and 71 kcal/mole for the O surface. Besides Zn and O atoms also Zn and O molecules are observed during the first heating cycle but only from the Zn surface. Complementary results are given for studies of surface conductivity. No superstructure has been found by LEED, even after various annealing treatments. However, step arrays with a height of one unit of the c axis (two double layers of atoms) are found on both types of polar surfaces. With increasing temperature of pretreatment the order of steps varies and the LEED contrast passes through a maximum.     

Diffusion von Protonen (Tritonen) in Eiskristallen

The diffusion coefficient of tritons in ice crystals has been measured at different temperatures between 0°C and ?35°C. The applied method excludes any surface diffusion. The absolute value of the diffusion coefficient at ?7°C was determined as 2·10^?11 cm²/sec (±10%) and the activation energy as 13,5 kcal/mole (±8%). The activation energy of proton (triton)-diffusion is therefore consistent with the activation energy found for the dielectric and mechanical relaxation of protons in ice. The importance of this consistency relative to the diffusion mechanism is discussed.     

The amount and location of amorphous component in polyethylene single crystals

Polyethylene single crystals from dilute solutions usually have a density ρ which is less than that of the ideal crystal lattice (ρ_c = 1.000 g/cm³). This density defect can be formally assigned to an “amorphous” component (1-α) = (ρ_c-ρ)/(ρ_c-ρa) and may be caused by vacancies in the crystal lattice and/or by the surface disorder connected with chain folds. The two-phase concept of single crystal structure assumes a very nearly ideal lattice core and two amorphous layers on the fold-containing surfaces. It is supported by density and heat content data of annealed samples, by small-angle X-ray scattering, by wide-line NMR investigations, and by the results of fuming nitric acid treatment.

The maximum thickness of the amorphous surface layer as a function of temperature may be estimated from the free energy requirement of such a layer. With regular chain folds one has a high concentration of gauche conformations yielding a high surface energy. The need for such a concentration disappears in the amorphous layer with loose loops. This gain in energy may be spent for surface melting. Still more important is the gain in entropy caused by the random distribution of loop lengths.     

Measurement of the adsorption energy on single crystal faces by field emission (hydrogen on tungsten)

As a preliminary study has shown¹), the isosteric energy of adsorption on single crystal faces can be measured, if the coverage is kept constant on controlling the field electron currents. This method has been improved (a) by the introduction of the probe hole technique, (b) by special cleaning procedures, and (c) by a more precise measurement of gas pressure and temperature. The method is used to obtain the adsorption energy q of hydrogen on the tungsten faces (100), (111), (112), (013), (122), (123) and (114). Initial q-values vary between 33 kcal/mole on (013) and 40 kcal/mole on (112). q decreases with coverage down to a few kcal/mole. The results indicate a relation between the adsorption states and the structure of each face.     

The adsorption of activated nitrogen on platinum single crystal faces

The adsorption of activated nitrogen on a stepped Pt(S)-[9(111) × (111)] face was investigated by LEED, AES and flash desorption. Nitrogen was supplied to the crystal from a high frequency discharge tube. For comparison some orienting measurements were also carried out on smooth (111) and (100) platinum faces. Activated nitrogen is adsorbed at room temperature on all three faces up to about half a monolayer coverage. No additional LEED patterns indicating long range order of the adsorbed layer were found. By flash heating a small desorption peak at 120°C and a large peak between 175 and 230°C depending on the initial coverage were observed on the (111) type faces. The desorption can be described approximately by a second order rate law with an energy of activation of 25± 3 kcal/mole. No influence of surface steps on the properties of the adsorbed layer was detected. On the (100) face two coverage independent desorption maxima at 120 and 170°C of about equal intensities were found.     

Angle-resolved photoemission from Fe(110): Determination of E()

Using angle-resolved photoemission spectroscopy utilizing polarized synchrotron radiation with a clean Fe(110) sample, we identified each of the Σ₁-, Σ₃- and Σ₄-band peaks with certainty using symmetry selection rules. We also determined energy band dispersion along the γ-Σ-N direction in the bulk Brillouin zone assuming direct transitions. There are small discrepancies between the observed bands and recent ground-state band calculations possibly due to Coulomb correlation effects. A surface state with odd symmetry about the [001] crystal direction and a binding energy of 0.15 eV at γ in the surface Brillouin zone was observed. Our results show that the ground-state calculations of ferromagnetic iron based on the local exchange correlation potential are basically in agreement with experimental dispersion relationship measurements.     

Binding states of zinc on the polar faces of Zno

The desorption of zinc from cleaved polar faces was investigated in UHV. TDS (calibrated by evaporation of metallic Zn), surface conductivity, LEED and AES were used. The initial sticking coefficient is lower on the Zn face than on the O face, 0.2 and 1 respectively. On both faces two states of adsorption occur. The lower state on the Zn face has an activation energy of 35 kcal/mole(1.5 eV). The corresponding energy on the oxygen face is 16 kcal/mole (0.7 eV). The lower peak is connected with an increase in surface conductivity on both faces. On the Zn face this surface conductivity can be attributed to a surface donor 1.3 eV above the conduction band edge. Above one monolayer the formation of islands and an epitactical growing of a zinc lattice were found.     

Infrared studies of crystallinity in poly(vinyl chloride)

The infrared spectrum of a solvent-cast film of commercial poly(vinyl chloride) (PVC) can be very sensitively compared to a rapidly quenched film of the same material by using a compensation technique. When this is done, crystalline bands, as seen in urea canal complex PVC, can be detected and measured in the solvent-cast film. The melting and recrystallization behavior as well as the broad melting range from 120° to 210°C indicate the presence of crystallites of widely different degrees of perfection. Crystallization kinetics from the quenched glassy state indicate that time-temperature superposition applies with an activation energy of 90 kcal/mole. Molecular mobility is indicated as the rate-controlling mechanism.     

Chlorine adsorption on the low index surfaces of silver: Energetics and structures

The interaction of Cl₂ with Ag single crystal surfaces has been studied over a range of crystal temperature and gas pressure. Observations have been made for the (111), (100) and (110) surfaces. Measured adsorption isobars for Ag(100) were used to obtain isosteric heats of adsorption; values ranged from ~ ?60 kcal/mole (of Cl₂) at low coverage to ~ ?70 kcal/mole near saturation. The structure formed by Cl₂ adsorption on (100) is believed to be a simple overlayer. For (110) and (111) the values obtained for the heat of adsorption were ~ ?55 kcal/mole. On Ag(111) an epitaxially oriented AgCl(111) is believed to form.     

Adsorption of hydrogen on palladium single crystal surfaces

The adsorption of hydrogen on clean Pd(110) and Pd(111) surfaces as well as on a Pd(111) surface with regular step arrays was studied by means of LEED, thermal desorption spectroscopy and contact potential measurements. Absorption in the bulk plays an important role but could be separated from the surface processes. With Pd(110) an ordered 1 × 2 structure and with Pd(111) a 1 × 1 structure was formed. Maximum work function increases of 0.36, 0.18 and 0.23 eV were determined with Pd(110), Pd(111) and the stepped surface, respectively, this quantity being influenced only by adsorbed hydrogen under the chosen conditions. The adsorption isotherms derived from contact potential data revealed that at low coverages θ ∞ √p_H2, indicating atomic adsorption. Initial heats of H₂ adsorption of 24.4 kcal/mole for Pd(110) and of 20.8 kcal/mole for Pd(111) were derived, in both cases E_ad being constant up to at least half the saturation coverage. With the stepped surface the adsorption energies coincide with those for Pd(111) at medium coverages, but increase with decreasing coverage by about 3 kcal/mole. D₂ is adsorbed on Pd(110) with an initial adsorption energy of 22.8 kcal/mole.     

Infrared studies of chain folding in polymers. VII. Amylose

Studies of chain folding in amylose employing spectroscopic techniques have led to an assignment of the 1295-cm^?1 band to a unique fold conformation. Irregular folds, present in single crystals, are regularized to the unique fold conformation during annealing. Annealing of solution-cast films, which initially contain a small amount of regular folding, increases the amount of regular folds. Swelling of these annealed films with water vapor destroys this unique folded conformation.     

The adsorption of hydrogen and the reaction of hydrogen with oxygen on Pt (100)

The adsorption of hydrogen on Pt (100) was investigated by utilizing LEED, Auger electron spectroscopy and flash desorption mass spectrometry. No new LEED structures were found during the adsorption of hydrogen. One desorption peak was detected by flash desorption with a desorption maximum at 160 °C. Quantitative evaluation of the flash desorption spectra yields a saturation coverage of 4.6 × 10¹⁴ atoms/cm² at room temperature with an initial sticking probability of 0.17. Second order desorption kinetics was observed and a desorption energy of 15–16 kcal/mole has been deduced. The shapes of the flash desorption spectra are discussed in terms of lateral interactions in the adsorbate and of the existence of two substates at the surface. The reaction between hydrogen and oxygen on Pt (100) has been investigated by monitoring the reaction product H₂O in a mass spectrometer. The temperature dependence of the reaction proved to be complex and different reaction mechanisms might be dominant at different temperatures. Oxygen excess in the gas phase inhibits the reaction by blocking reactive surface sites. At least two adsorption states of H₂O have to be considered on Pt (100). Desorption from the prevailing low energy state occurs below room temperature. Flash desorption spectra of strongly bound H₂O coadsorbed with hydrogen and oxygen have been obtained with desorption maxima at 190 °C and 340 °C.     

Application of semiclassical collision theory to the collinear reactive H+H2 system

Semiclassical collision theory using the stationary-phase method and the near classical method was applied to the collinear H+H₂ system, in the (total) energy range E = 12·5-30 kcal/mole. It was found that although the near classical method was applicable in the near-threshold energy range of E = 13-17 kcal/mole, and both methods gave qualitatively correct results for E > 17 kcal/mole, yet there was no good quantitative agreement with the exact results.