Vibrationally assisted diffusion of H2O and D2O on Pd(1 1 1)

The adsorption and diffusion of isolated H₂O and D₂O molecules on Pd(1 1 1) were studied using scanning tunneling microscopy at low temperature (∼40 K). At low tunneling voltage the diffusion is thermally activated. The diffusion rate is enhanced by several orders of magnitude when the tunneling electron has enough energy to excite the vibrational “scissor” mode of the molecule. An isotope effect was observed in the threshold voltage for electron-assisted diffusion of H₂O and D₂O.     

Chemical reactions of water molecules on Ru(0 0 0 1) induced by selective excitation of vibrational modes

Tunneling electrons in a scanning tunneling microscope were used to excite specific vibrational quantum states of adsorbed water and hydroxyl molecules on a Ru(0 0 0 1) surface. The excited molecules relaxed by transfer of energy to lower energy modes, resulting in diffusion, dissociation, desorption, and surface-tip transfer processes. Diffusion of H₂O molecules could be induced by excitation of the O-H stretch vibration mode at 445 meV. Isolated molecules required excitation of one single quantum while molecules bonded to a C atom required at least two quanta. Dissociation of single H₂O molecules into H and OH required electron energies of 1 eV or higher while dissociation of OH required at least 2 eV electrons. In contrast, water molecules forming part of a cluster could be dissociated with electron energies of 0.5 eV.     

Isotope effect in the vibrational spectra of water measured in experiments with a scanning tunneling microscope

The vibrational frequencies of adsorbed H₂O and D₂O molecules are measured under high-vacuum conditions by in-cavity scanning tunneling spectroscopy. An isotope effect is observed. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 1, 37–39 (10 July 1997)     

Local mode vibrations of water

Classical trajectory calculations on a realistic potential for the stretching vibrations of the water molecule are used to demonstrate the existence of stable local vibrational modes, which occur in degenerate pairs. The proportion of phase space occupied by such modes increases with increasing energy, with a clearly characterized (0, 2) local state in a local quantum number assignment. It is argued that quantum mechanical corrections will lead to a local mode splitting which is predicted to decrease in magnitude along any given stretching vibrational progression, and to be larger for a given quantum state of D₂O than for H₂O.     

Electronic excitation of ice monomers on Au(111) by scanning tunneling microscopy

Scanning tunneling microscopy, inelastic tunneling spectroscopy, and electron induced manipulation are used to investigate electronic excitation of D₂O monomers and small clusters adsorbed at the elbows of the Au(111) reconstruction. Diffusion of molecules, dissociation of clusters, and rearrangement of the reconstruction is induced by electronic excitation. Threshold energies of between 200 and 250 meV and of 446 meV are explained by combined vibrational modes of D₂O molecules. External vibrational modes of D₂O molecules on Au(111) are identified by inelastic tunneling spectroscopy at ≈18, 30, and 41 meV.     

The assignment of quantum numbers in the theoretical spectra of the H2 16O, H2 17O, and H2 18O molecules calculated by variational methods in the region 0–26000 cm−1

Quantum numbers have been assigned in the theoretical spectra of three isotopologues of the water molecule: H₂ ¹⁶O, H₂ ¹⁷O, and H₂ ¹⁸O. The spectra were calculated by variational methods in the region 0–26000 cm^?1 at a temperature of 296 K. For each molecule, the quantum numbers are assigned to more than 28000 levels. The quantum numbers are assigned to 216766, 210679, and 211073 spectral lines of the H₂ ¹⁶O, H₂ ¹⁷O, H₂ ¹⁸O molecules, respectively. The theoretical spectra with the assigned quantum numbers are available in the Internet.     

Solvatochromic Studies of Fluorescein Dianion in N,N-Dimethylformamide/Water and Dimethylsulphoxide/Water Mixtures

Abstract

The absorption, excitation and fluorescence spectra of the fluorescein dianion (FL^2?) in N, N-Dimethylformamide (DMF)/water (H₂O) and Dimethylsulphoxide (DMSO)/H₂O solvent mixtures have been investigated. It is found that the absorption λ_max and emission maxima EX, _nax are both hypsochromic shifted when the H₂O content in the solvent mixtures increases. However, the shoulder peaks λ_s remain constant at 483. 5nm within the range of H₂O mole fraction, x= 0 to 0. 518 in a DMF/H₂O solvent mixture and at 484. 4nm within the range, x=0 to 0. 304, in a DMSO/H₂O mixture. Further increases in H₂O content, cause a hypsochromic shift in λ_s. The molar energies for the electronic transition from the ground state (S₀) to S₁, the first excited singlet state, (E_T(1)) and to S₂, the 2nd excited singlet state, (E_T(2)) of FL^2?in the solvent mixtures are also plotted against x. Linear straight lines and intersection points are observed at x=0. 73 for E_T(1) and at x=0. 51 for E_T(2) in the DMF/H₂O mixture and at x=0. 71 for E_T(1) and at x=0. 31 &; 0. 69 for E_T(2) in the DMSO/H₂O mixture. Hydrogen-bonding stabilization effects are used to explain the above observations. The variation in relative fluorescence quantum yields of S₁ and S₂ of FL^2? with x in the aprotic solvent-H₂O mixtures to FL^2? in pure aprotic solvent are determined and discussed.     

Critical evaluation of measured rotation–vibration transitions and an experimental dataset of energy levels of HD18O

All available transitions from microwave to visible region (0.2–12 105 cm^?1) of the HD¹⁸O molecule were collected and tested using the RITZ computer code. Literature data were completed by transitions assigned to HD¹⁸O in long path Fourier transform absorption spectra of the H₂O, HDO and D₂O gas mixtures with natural abundance of oxygen-18. In addition about 40 unassigned lines between 4200 and 6600 cm^?1 of our previous water study associated with the HD¹⁸O molecule have been found and assigned. The new long path absorption spectra of the HDO and D₂O mixtures allow us to observe about 1000 transitions of HD¹⁸O in the 6125–10 720 cm^?1 spectral region. These data have been critically analyzed and used to obtain the most complete and precise set of the experimental energy levels of this molecule.     

Far-infrared absorption intensities of H2O and D2O in C6H6

Far-i.r. absorption intensities have been measured for H₂O and D₂O in C₆H₆ solutions. Beer's law plots were found to be nonlinear. From the plots, the equilibrium constants of dimer formation in benzene were estimated to be 2.4M^-1 and 3.3M^-1 for H₂O and D₂O at 20°C, respectively. Based on Onsager's reaction field and including explicitly the effect of differences in molecular size between solute and solvent molecules, the internal moment of a water molecule and the volume ratio of a molecule to a cavity were estimated from the integrated absorption intensity of a D₂O monomer in C₆H₆ as 1.98 D and 0.7, respectively     

Isotope effect and cluster size dependence for water and hydrated hydrogen halide clusters: multi-component molecular orbital approach

In order to explore the proton/deuteron (H/D) isotope effect on the structures, wavefunctions, and size dependence of water clusters, both electronic and nuclear wavefunctions are determined simultaneously. The optimized centres and the exponents for the nuclear orbitals indicate the Ubbelohde effect, i.e. the deuteron has weaker hydrogen bonding than the proton. Calculations are made also of hydrogen halide water clusters, Such as HF(H₂O)_n, HB_r(H₂O)_n, (n = 0–4), and their deuterated species. Only the hydrogen transferred ring structure is optimized for the protonic HBr (H₂O)₃ cluster, while both the hydrogen transferred and the non-transferred structures are obtained for the deuterated DBr (H₂O)₃ cluster under the one-particle multi-component treatment. The proton in the HF molecule is localized more than those in the HCl and HBr molecules, and no hydrogen transferred structures are obtained for HF water clusters.     

Resonant scattering of phonons by adsorbates on clean silicon surfaces

We used Phonon Surface Scattering Spectroscopy (PSSS) to study excitations of adsorbates in the far infrared region from 100 eV up to 3 meV. We investigated the scattering of pulses of monochromatic phonons by thin films of H₂O, D₂O and Ne deposited in situ onto laserannealed Si(100)-surfaces. For all substances we observed a broad scattering at coverages below one monolayer and a strong resonant scattering at about 3 monolayers. The resonance frequency decreased with increasing coverage. The reasons for the resonances are discussed. Because of the lack of any observable isotope effect between H₂O and D₂O, the possibility of tunneling states in these layers can be excluded. Instead, we conclude that a lateral vibrational mode of the adlayer is responsible for the resonance effect. Corresponding calculations by means of continuum elasticity theory describe the scattering behaviour very well if similar elastic constants are used for all film substances.     

Adsorption behavior of H2O on clean and oxygen precovered Ni(s)(111)

Photoelectron spectroscopy (UPS), thermal desorption spectroscopy (TDS), isotope exchange experiments, work function change (δφ) and LEED were used to study the adsorption and dissociation behavior of H₂O on a clean and oxygen precovered stepped Ni(s)[12(111) × (111)] surface. On the clean Ni(111) terraces fractional monolayers of H₂O are adsorbed weakly in a single adsorption state with a desorption peak temperature of 180 K, just above that of the ice multilayer desorption peak (T_m = 155 K). In the angular resolved UPS spectra three H₂O induced emission maxima at 6.2, 8.5 and 12.3 eV below E_F were found for θ ≈ 0.5. Angular and polarization dependent UPS measurements show that the C_2v symmetry of the H₂O gas-phase molecule is not conserved for H₂O(ad) on Ni(s)(111). Although the Δφ suggest a bonding of H₂O to Ni via the negative end of the H₂O dipole, the O atom, no hints for a preferred orientation of the H₂O molecular axes were found in the UPS, neither for the existence of water dimers nor for a long range ordered H₂O bilayer. These results give evidence that the molecular H₂O axis is more or less inclined with respect to the surface normal with an azimuthally random distribution. H₂O adsorption at step sites of the Ni(s)(111) surface leads in TDS to a desorption maximum at T_m = 225 K; the binding energy of H₂O to Ni is enhanced by about 30% compared to H₂O adsorbed on the terraces. Oxygen precoverage causes a significant increase of the H₂O desorption energy from the Ni(111) terraces by about 50%, suggesting a strong interaction between H₂O and O(ad). Work function measurements for H₂O+O demonstrate an increase of the effective H₂O dipole moment which suggests a reorientation of the H₂O dipole in the presence of O(ad), from inclined to a more perpendicular position. Although TDS and Δφ suggest a significant lateral interaction between H₂O+O(ad), no changes in the molecular binding energies in UPS and no “isotope exchange” between ¹⁸O(ad) and H₂¹⁶O(ad) could be observed. Also, dissociation of H₂O could neither be detected on the oxygen precovered Ni(s)(111) nor on the clean terraces.     

Ultraviolet radiation sources on (H2O,D2O) water vapor

Emission characteristics of ultraviolet (UV) radiation from water vapor (H₂O, D₂O, and a mixture of H₂O and D₂O vapors) excited by pulse-periodic discharges with open electrodes, as well as electrodes outside the discharge tube (capacitive discharge), are presented. Radiation is studied in a spectral range of 175–350 nm. The emission characteristics of a UV radiation source based on vapors of ordinary and “heavy” water, as well as the results of optimization of brightness of radiation bands from the OH and OD radicals as functions of pressure and the composition of the He-H₂O and He-D₂O mixtures, are reported.     

The fluctuation hypothesis of hydrogen bonding

To describe the distortion perturbations of the water molecules in solutions the quantum-mechanical method of partial oscillators has been developed. This method allows one to separate in a simple manner two types of influences on vibrations of OH oscillators, viz. the intermolecular perturbations resulting in the different strengths of hydrogen bonds and intramolecular coupling between stretching vibrations. Here the coupling is treated quite strictly, whereas the intermolecular perturbations are introduced phenomenologically. The calculation of the distribution of distortions among molecules in liquid H₂O and D₂O induced by non-equivalency of the two hydrogen bonds of the water molecule has been made on the basis of the method developed, and the parameters of the mean statistical molecule have been found from the experimental spectrum of HOD. The depolarization ratios of vibrations in Raman spectra of the mean statistical molecules H₂O and D₂O have been computed as an illustration of the possibilities of the proposed calculation method. All the estimates show that the stretching oscillators of H₂O and D₂O molecules are significantly coupled in spite of the great distortion of the symmetry of water molecules in the liquid state.     

Azurin-Solvent interaction: an ESR spin labeling investigation

We have investigated by means of electron spin resonance (ESR) spectroscopy using two spin labels, Iodoacetamido-proxyl and 3-Maleimido-proxyl, the dynamics of two different regious around the active site of azurin, a copper containing blue protein. The ESR measurements of spin labeled azurin have been carried out in the 110–300 K temperature range on wet (H₂O, D₂O and ethanol/water mixtures) and lyophilized samples. The behaviours of the outer hyperfine splitting separation, 2A′ _zz , of the ESR spectravs temperature of the lyophilized, and fully hydrated azurin in H₂O and D₂O suggest that the two spin labels are located in regions of the protein surface with different dynamics and polarity. Moreover, all differences in the 2A′ _zz values shown by the spin labeled azurin in normal and heavy water as well as the temperature behaviour disappear when azurin is in ethanol/water mixtures. The results are discussed in terms of a close correlation between the molecular dynamics of the protein fragments to which the two spin labels are bound and the properties of the solvent used.     

Electromigration and permeation of hydrogen and deuterium in silver

A steady state flow technique was used to measure the effective charge number (Z*) and permeability (N) of hydrogen and deuterium in silver. Over the range of temperature (485–720°C) and pressure (220–750 torr) the effective charge number is a constant. The interstitial impurity migrates in the direction of the electron wind with Z_H* = ?6·8 and Z_D* = ? 18. The values of Z* are of the same order as self-electromigration but the size of the isotope effect is surprising. The quantum theories used to explain the isotope effect for hydrogen electromigration in Fe and Ni appear to fail here. In order to determine the effective charge number is was necessary to measure the permeability. For both H₂ and D₂, the permeability in silver follows the equation N = N_O exp(? Q/RT) where N_0D = 2·39 ± 0·40, Q_D = 14400 ± 300, N_OH = 2·86 ± 0·70 and Q_H = 14200 ± 500. Here Q is in units of cal/mol and N is in units of cc(ntp)/(sec - atm² - cm) The isotope effect ratio N_H/N_D = 1·25 was smaller than the classically expected value of (2)^1/2, but could be explained by the theory of Ebisuzaki, Kass and O'Keeffe.     

Stereodynamics of chemical reactions: quasi-classical,quantum and mixed quantum-classical theories

In this review, some benchmark works by Han and coworkers on the stereodynamics of typical chemical reactions, triatomic reactions H + D₂, Cl + H₂ and O + H₂ and polyatomic reaction Cl+CH₄/CD₄, are presented by using the quasi-classical, quantum and mixed quantum-classical methods. The product alignment and orientation in these A+BC model reactions are discussed in detail. We have also compared our theoretical results with experimental measurements and demonstrated that our theoretical results are in good agreement with the experimental results. Quasi-classical trajectory (QCT) method ignores some quantum effects like the tunneling effect and zero-point energy. The quantum method will be very time-consuming. Moreover, the mixed quantum-classical method can take into account some quantum effects and hence is expected to be applicable to large systems and widely used in chemical stereodynamics studies.     

High temperature thermodynamics of H2 and D2 in titanium,and in dilute titanium oxygen solid solutions

The Tian Calvet microcalorimetric method has been improved in order to determine Δ$\text{H}$_H(D), the partial molar enthalpy of mixing of hydrogen (deuterium) in the Ti-H₂(D₂) solid systems for compositions 0 < (H/Ti) < 1.85, at 713 K and in the α TiO_y + H₂ solid solutions (y = (O/Ti)) at 745 K. The combined calorimetric and equilibrium method allows a precise evaluation of the partial molar entropies. The results of this study differ substantially from earlier published data.     

Investigations of multiphoton selective dissociation of (CH3)2O in the field of a pulsed CO2 laser

Experimental investigations of multiphoton selective dissociation of (CH₃)₂O induced by a pulsed CO₂ laser have been conducted. Separation of H, C, and O isotopes was performed in enriched mixtures and in samples with the natural abundance. The following coefficients of selectivity have been obtained:K _D/K_H=4.0,K ₁₃/K₁₂=1.7, andK ₁₈/K₁₆≧1.6. We studied the dependences of the selectivity coefficient on ether pressure, on the laser energy and frequency as well as the influence of secondary chemical reactions on the dissociation selectivity. Estimations made by using the RRKM theory have indicated that ether molecules that decompose have an average excitation energy above the dissociation threshold of ∼1.5 kcal/mole.     

Theoretical studies on the adsorption and decomposition of H2O on Pd(1 1 1) surface

To provide information about the chemistry of water on Pd surfaces, we performed density functional slab model studies on water adsorption and decomposition at Pd(1 1 1) surface. We located transition states of a series of elementary steps and calculated activation energies and rate constants with and without quantum tunneling effect included. Water was found to weakly bind to the Pd surface. Co-adsorbed species OH and O that are derivable from H₂O stabilize the adsorbed water molecules via formation of hydrogen bonds. On the clean surface, the favorable sites are top and bridge for H₂O and OH, respectively. Calculated kinetic parameters indicate that dehydrogenation of water is unlikely on the clean regular Pd(1 1 1) surface. The barrier for the hydrogen abstraction of H₂O at the OH covered surface is approximately 0.2-0.3 eV higher than the value at the clean surface. Similar trend is computed for the hydroxyl group dissociation at H₂O or O covered surfaces. In contrast, the O-H bond breaking of water on oxygen covered Pd surfaces, H₂O_ad + O_ad → 2OH_ad, is predicted to be likely with a barrier of ∼0.3 eV. The reverse reaction, 2OH_ad → H₂O_ad + O_ad, is also found to be very feasible with a barrier of ∼0.1 eV. These results show that on oxygen-covered surfaces production of hydroxyl species is highly likely, supporting previous experimental findings.