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5-Iodouracil (5-IU) can be integrated into DNA and acts as a UV sensitive chromophore suitable for probing DNA structure and DNA-protein interactions based on the photochemical reactions of 5-IU. Here, we perform joint studies of time-resolved Fourier transform infrared (TR-FTIR) spectroscopy and ab initio calculations to examine the state-specific photochemical reaction mechanisms of the 5-IU. The fact that uracil (U) is observed in TR-FTIR spectra after 266 nm irradiation of 5-IU in acetonitrile and ascribed to the product of hydrogen abstraction by the uracil-5-yl radical (U.) provides experimental evidence for the C--I bond homolysis of 5-IU. The excited state potential energy curves are calculated with the complete active space second-order perturbation//complete active space selfconsistent field method, from which a singlet predissociation mechanism is elucidated. It is shown that the initially populated 1(ππ*) state crosses with the repulsive 1(πσ*) or 1(nIσ*) state, through which 5-IU undergoes dissociation to the fragments of (U.) radical and iodine atom. In addition, the possibility of intersystem crossing (ISC) is evaluated based on the calculated vertical excitation energies. Although a probable ISC from 1(ππ*) state to 3(nOπ*) and then to the lowest triplet 3(ππ*) could occur in principal, there is little possibility for the excited state populations bifurcating to triplet manifold, given that the singlet state predissociation follows repulsive potential and should occur within dozens to hundreds of femtoseconds. Such low population of triplet states means that the contribution of triplet state to photoreactions of 5-IU should be quite minor. These results demonstrate clearly a physical picture of C--I bond homolysis of 5-IU and provide mechanistic illuminations to the interesting applications of 5-IU as photoprobes and in radiotherapy of cancer. [ABSTRACT FROM AUTHOR]

We augment ab initio molecular dynamics simulations with a quantitative account of phononic dissipation to study the non-equilibrium aftermath of the exothermic oxygen dissociation at lowindex (111), (100), and (110) Pd surfaces. Comparing the hyperthermal diffusion arising from a non-instantaneous dissipation of the released chemical energy, we find a striking difference in the resulting "hot" adatom lifetime that is not overall reflected in experimentally recorded product end distances. We rationalize this finding through a detailed mode-specific phonon analysis and identify the dominant dissipation channels as qualitatively different groups of localized surface modes that ultimately lead to intrinsically different rates of dissipation to the Pd bulk. The thus obtained first-principles perspective on non-equilibrium adsorbate-phonon dynamics thereby underscores the sensitive dependence on details of the phononic fine structure, while questioning prevalent assumptions about energy sinks made in commonly used model bath Hamiltonians. [ABSTRACT FROM AUTHOR]

Structural properties of brushes which are composed of weak acidic and basic polyelectrolytes are studied in the framework of a particle-based approach that implicitly accounts for the solvent quality. Using a semi-grandcanonical partition function in the framework of the Single-Chain-in-Mean-Field (SCMF) algorithm, the weak polyelectrolyte is conceived as a supramolecular mixture of polymers in different dissociation states, which are explicitly treated in the partition function and sampled by the SCMF procedure. One obtains a local expression for the equilibrium acid-base reaction responsible for the regulation of the charged groups that is also incorporated to the SCMF sampling. Coupled to a simultaneous treatment of the electrostatics, the approach is shown to capture the main features of weak polyelectrolyte brushes as a function of the bulk pH in the solution, the salt concentration, and the grafting density. Results are compared to experimental and theoretical works from the literature using coarse-grained representations of poly(acrylic acid) (PAA) and poly(2-vinyl pyridine) (P2VP) polymer-based brushes. As the Born self-energy of ions can be straightforwardly included in the numerical approach, we also study its effect on the local charge regulation mechanism of the brush. We find that its effect becomes significant when the brush is dense and exposed to high salt concentrations. The numerical methodology is then applied (1) to the study of the kinetics of collapse/swelling of a P2VP brush and (2) to the ability of an applied voltage to induce collapse/swelling of a PAA brush in a pH range close to the pKa value of the polymer. [ABSTRACT FROM AUTHOR]

Threshold collision-induced dissociation using a guided ion beam tandem mass spectrometer is performed on (N2H4)H+(H2O)n, where n = 1 and 2, and on the protonated unsymmetrical 1, 1-dimethylhydrazine one-water complex. The primary dissociation pathway for all clusters is a loss of a single water molecule, which for n = 2 is followed by the sequential loss of an additional water molecule at higher collision energies. The data are analyzed using a statistical model after accounting for internal and kinetic energy distributions, multiple collisions, and kinetic shifts to obtain 0 K bond dissociation energies (BDEs). These are also converted using a rigid rotor/harmonic oscillator approximation to yield thermodynamic values at room temperature. Experimental BDEs compare favorably to theoretical BDEs determined at the B3LYP, M06, mPW1PW91, PBE0, MP2(full), and CCSD(T) levels of theory with a 6-311+G(2d,2p) basis set both with and without empirical dispersion. These calculations also allow visualization of the structures of these complexes, which are simple hydrogenbonded donor-acceptors. [ABSTRACT FROM AUTHOR]

• The role of supported Au and Pd in oxygen activation under irradiation. • Dissociation of O 2 evidenced by NAP-XPS and in-situ spectroscopy. • Both Au and Pd prolong the lifetime of reactive oxygen species. • Au bonds O atom stronger and promotes the selective oxidation. • Pd bonds O atom weaker and promotes the complete oxidation. Activation of molecular oxygen plays an important role in photocatalytic selective oxidation reactions and complete degradation of organic pollutants. Noble metal cocatalysts are often employed to modulate the activation of oxygen to reach an optimum photocatalytic performance. However, the role of the metal nanoparticles (NPs) still remains unclear and deserves investigation for the design of efficient photocatalysts. Here, Au and Pd NPs are deposited on the TiO 2 photocatalyst to study the promotional mechanism of O 2 dissociation with the presence of glycerol under irradiation by near-ambient-pressure photoelectron spectroscopy and in-situ spectrometry approaches. While both Au and Pd NPs can dissociate O 2 into activated oxygen species, a relatively strong bonds of dissociated oxygen atom is observed on Au NPs than on the Pd NPs. This results in a moderate reduction rate of O 2 and eventually favors a mild oxidation reaction process for Au, and a rapid reduction rate of O 2 and eventually a deep oxidation reaction process for Pd, respectively. [Display omitted] [ABSTRACT FROM AUTHOR]

Many metal ions have been found to exert electrophilic effects on the dissociation of complexes and it has been proposed that a ternary intermediate is formed involving the complex and metal ion through the severing of one of the metal ligand bonds.To investigate this aspect, the dissociation of Fe(phen)3 2+ and effects of metal ion like Co2+ in the presence of SDS micelles providing anionic micellar surface. These results confirm that the formation of such a ternary intermediate and marked micellar catalysis of the reaction [ABSTRACT FROM AUTHOR]

Sequence-specific binding of proteins to DNA is essential for accessing genetic information. We derive a model that predicts an anticorrelation between the macroscopic association and dissociation rates of DNA binding proteins. We tested the model for thousands of different lac operator sequences with a protein binding microarray and by observing kinetics for individual lac repressor molecules in single-molecule experiments. We found that sequence specificity is mainly governed by the efficiency with which the protein recognizes different targets. The variation in probability of recognizing different targets is at least 1.7 times as large as the variation in microscopic dissociation rates. Modulating the rate of binding instead of the rate of dissociation effectively reduces the risk of the protein being retained on nontarget sequences while searching. [ABSTRACT FROM AUTHOR]

To reduce carbon dioxide (CO2) emissions at room temperature and atmospheric pressure, CO2 reduction to carbon monoxide (CO) by nonthermal plasma (NTP) is performed. In liquefied natural gas (LNG) gas-turbine combined power generation plant that have high power generation efficiency, the CO2self-consistency including the power plant can be achieved if the energy efficiency of CO2 reduction by NTP is at least 49%. In this study, CO2 reduction performance is evaluated by two processes using different gas mixtures. First, CO2 is adsorbed from a gas flow mixture of argon (Ar) or helium (He), nitrogen (N2), and CO2 (~10% concentration) by the adsorbent; second, CO2 is desorbed and reduced by Ar or He NTP flow at a higher concentration of 10 to 22% under all experimental conditions. The energy efficiency increases with the elapsed time and reaches 8−12%. The efficiency increases as Ar / (Ar + N2) ×100 takes further away from 50%, and He / (He + N2) × 100 takes a lower value. Under all conditions, a part of CO obtained by reduction is further reduced to atomic carbon. If reduction to atomic carbon is taken into account, the energy efficiency significantly increases from 8−12% to 16−22%. The efficiency increases with the higher concentration of Ar and lower concentration of He. [ABSTRACT FROM AUTHOR]

The verification of probabilistic forecasts in hydro-climatology is integral to their development, use, and adoption. We propose here a means of utilizing goodness of fit measures for verifying the reliability of probabilistic forecasts. The difficulty in measuring the goodness of fit for a probabilistic prediction or forecast is that predicted probability distributions for a target variable are not stationary in time, meaning one observation alone exists to quantify goodness of fit for each prediction issued. Therefore, we suggest an additional dissociation that can dissociate target information from the other time variant part--the target to be verified in this study is the alignment of observations to the predicted probability distribution. For this dissociation, the probability integral transformation is used. To measure the goodness of fit for the predicted probability distributions, this study uses the root mean squared deviation metric. If the observations after the dissociation can be assumed to be independent, the mean square deviation metric becomes a chi-square test statistic, which enables statistically testing the hypothesis regarding whether the observations are from the same population as the predicted probability distributions. An illustration of our proposed rationale is provided using the multi-model ensemble prediction for El Niño-Southern Oscillation. [ABSTRACT FROM AUTHOR]

The King and Wells molecular beam reflectivity method has been used for a quantum state resolved study of the dissociative chemisorption of CH4 on Pt(111) at several surface temperatures. Initial sticking coefficients S0 were measured for incident CH4 prepared both with a single quantum of ν3 antisymmetric stretch vibration by infrared laser pumping and without laser excitation. Vibrational excitation of the ν3 mode is observed to be less efficient than incident translational energy in promoting the dissociation reaction with a vibrational efficacy ην3 = 0.65. The initial state resolved sticking coefficient Sν30 was found to be independent of the surface temperature over the 50 kJ/mol to 120 kJ/mol translational energy range studied here. However, the surface temperature dependence of the King and Wells data reveals the migration of adsorbed carbon formed by CH4 dissociation on the Pt(111) surface leading to the growth of carbon particles. [ABSTRACT FROM AUTHOR]

The cavitation of gas bubbles in liquids has been applied to different disciplines in life and natural sciences, and in technologies. To obtain an appropriate theoretical description of effects induced by the bubble cavitation, we develop an all-atom nonequilibrium molecular-dynamics simulation method to simulate bubbles undergoing harmonic oscillation in size. This allows us to understand the mechanism of the bubble cavitation-induced liquid shear stress on surrounding objects. The method is then employed to simulate an Aß fibril model in the presence of bubbles, and the results show that the bubble expansion and contraction exert water pressure on the fibril. This yields to the deceleration and acceleration of the fibril kinetic energy, facilitating the conformational transition between local free energy minima, and leading to the dissociation of the fibril. Our work, which is a proof-of-concept, may open a new, efficient way to dissociate amyloid fibrils using the bubble cavitation technique, and new venues to investigate the complex phenomena associated with amyloidogenesis. [ABSTRACT FROM AUTHOR]

Improving reactivity on an insulating surface is crucial due to its important applications in surface catalytic reactions. In this work, we carried out first-principles calculations to investigate the adsorption of O2 on a single-layer MgO(100) film deposited on a metal substrate. The adsorption configurations, reaction pathways, molecular dynamics simulations, and electronic properties are reported. We reveal that O2 can completely dissociate on the surface, which is in sharp contrast to that on MgO(100) films thicker than one monolayer. The dissociated O2 tends to penetrate into the interfacial region, behaving like a switch to trigger subsequent chemical reactions. As an example, the interplay between water and the interfacial oxygen results in the formation of hydroxyl radicals. This study paves an avenue to accomplish the desired surface catalytic reactions, especially those involving oxygen. [ABSTRACT FROM AUTHOR]

The internal energy transferred when projectile molecular ions of naphthalene collide with argon gas atoms was extracted from the APCI-CID (atmospheric-pressure chemical ionization collisioninduced dissociation) mass spectra acquired as a function of collision energy. Ion abundances were calculated by microcanonical integration of the differential rate equations using the Rice-Ramsperger-Kassel-Marcus rate constants derived from a UB3LYP/6-311G+(3df,2p)//UB3LYP/6-31G(d) fragmentation mechanism and thermal-like vibrational energy distributions pM (E,dTchar). The mean vibrational energy excess of the ions was characterized by the parameter dTchar ("characteristic temperature"), determined by fitting the theoretical ion abundances to the experimental breakdown graph (a plot of relative abundances of the ions as a function of kinetic energy) of activated naphthalene ions. According to these results, the APCI ion source produces species below dTchar = 1457 K, corresponding to 3.26 eV above the vibrational ground state. Subsequent collisions heat the ions up further, giving rise to a sigmoid curve of dTchar as a function of Ecom (center-of-mass-frame kinetic energy). The differential internal energy absorption per kinetic energy unit (dEvib/dEcom) changes with Ecom according to a symmetric bell-shaped function with a maximum at 6.38 « 0.32 eV (corresponding to 6.51 « 0.27 eV of vibrational energy excess), and a half-height full width of 6.30 « 1.15 eV. This function imposes restrictions on the amount of energy that can be transferred by collisions, such that a maximum is reached as kinetic energy is increased. This behavior suggests that the collisional energy transfer exhibits a pronounced increase around some specific value of energy. Finally, the model is tested against the CID mass spectra of anthracene and pyrene ions and the corresponding results are discussed. [ABSTRACT FROM AUTHOR]

Efficient multiple exciton generation (MEG) in chiral single-wall carbon nanotubes (SWCNTs) is present within the solar spectrum range as shown by the many-body perturbation theory calculations combined with the density functional theory simulations. To describe the impact ionization process, we calculate exciton-to-biexciton decay rates R1×2 and biexciton-to-exciton rates R2→1 in the (6,2) and (10,5) SWCNTs. Within the solar energy range, we predict R1→2 ~ 1014 s-1, while biexciton-to-exciton recombination is weak with R2→1/R1→2 ≤ 10-2. Also we calculate quantum efficiency (QE), the average number of excitons created by a single absorbed photon, for which we find QE ≃ 1.2-1.6, that is 20%-60%. However, MEG strength in these SWCNTs varies strongly with the excitation energy due to highly non-uniform density of states at the low energy. We hypothesize that MEG efficiency in the chiral SWCNTs can be enhanced by altering the low-energy electronic spectrum via surface functionalization, or by mixing SWCNTs of different chiralities. [ABSTRACT FROM AUTHOR]

We propose improvements to our evolutionary algorithm (EA) [J. M. C. Marques and F. B. Pereira, J. Mol. Liq. 210, 51 (2015)] in order to avoid dissociative solutions in the global optimization of clusters with competing attractive and repulsive interactions. The improved EA outperforms the original version of the method for charged colloidal clusters in the size range 3 ≤ N ≤ 25, which is a very stringent test for global optimization algorithms. While the Bernal spiral is the global minimum for clusters in the interval 13 ≤ N ≤ 18, the lowest-energy structure is a peculiar, so-called beaded-necklace, motif for 19 ≤ N ≤ 25. We have also applied the method for larger sizes and unusual quasi-linear and branched clusters arise as low-energy structures. [ABSTRACT FROM AUTHOR]

We have performed calculations on the dissociative chemisorption of H2 on un-reconstructed and reconstructed Au(111) with density functional theory, and dynamics calculations on this process on un-reconstructed Au(111). Due to a very late barrier for dissociation, H2 + Au(111) is a candidate H2-metal system for which the dissociative chemisorption could be considerably affected by the energy transfer to electron-hole pairs. Minimum barrier geometries and potential energy surfaces were computed for six density functionals. The functionals tested yield minimum barrier heights in the range of 1.15-1.6 eV, and barriers that are even later than found for the similar H2 + Cu(111) system. The potential energy surfaces have been used in quasi-classical trajectory calculations of the initial (v,J) state resolved reaction probability for several vibrational states v and rotational states J of H2 and D2. Our calculations may serve as predictions for state-resolved associative desorption experiments, from which initial state-resolved dissociative chemisorption probabilities can be extracted by invoking detailed balance. The vibrational efficacy ηv=0→1 reported for D2 dissociating on un-reconstructed Au(111) (about 0.9) is similar to that found in earlier quantum dynamics calculations on H2 + Ag(111), but larger than found for D2 + Cu(111). With the two functionals tested most extensively, the reactivity of H2 and D2 exhibits an almost monotonic increase with increasing rotational quantum number J. Test calculations suggest that, for chemical accuracy (1 kcal/mol), the herringbone reconstruction of Au(111) should be modeled. [ABSTRACT FROM AUTHOR]

Optically detected single-turnover measurements of biological and inorganic catalysts provide a detailed picture of structural and dynamical influences on catalytic activity. Measurement at the single-molecule level of catalysis of a fluorogenic reaction (or its reverse) yields a stochastic fluorescence trajectory reflecting the statistics of individual reaction and product dissociation events. Analysis of time correlations displayed by this trajectory reveals reaction details inaccessible in a bulk measurement of averaged dynamics. Superresolution optical detection techniques can provide a spatial resolution over which correlations could be observed in space as well as time. A model is constructed here for spatial correlations in catalytic activity produced by an entity transported among multiple active sites. An approximation strategy based on perturbation theory in the coupling between transport and reaction dynamics is applied to calculate the mean dwell time of a reactant on an active site and the correlation between dwell times of reactants at different locations. [ABSTRACT FROM AUTHOR]

Electron transfer in collisions between low-n, n = 12, Rydberg atoms and targets that attach lowenergy electrons can lead to the formation of heavy-Rydberg ion-pair states comprising a weaklybound positive-negative ion pair that orbit each other at large separations. Measurements of the velocity and angular distribution of ion-pair states produced in collisions with 1,1,1-C2Cl3F3, CBrCl3, BrCN, and Fe(CO)5 are used to show that electron transfer reactions furnish a new technique with which to examine the lifetime and decay energetics of the excited intermediates formed during dissociative electron capture. The results are analyzed with the aid of Monte Carlo simulations based on the free electron model of Rydberg atom collisions. The data further highlight the capabilities of Rydberg atoms as a microscale laboratory in which to probe the dynamics of electron attachment reactions. [ABSTRACT FROM AUTHOR]

We investigate ionization at a solid-water interface in an applied electric field. We attach an electrode to a dielectric film bearing silanol or carboxyl groups with an areal density Γ0, where the degree of dissociation α is determined by the proton density in water close to the film. We show how α depends on the density n0 of NaOH in water and the surface charge density sm on the electrode. For σm > 0, the protons are expelled away from the film, leading to an increase in α. In particular, in the range 0 < σm < eΓ0, self-regulation occurs to realize α ≌ σm/eΓ0 for n0 ≪ nc, where nc is 0.01 mol/L for silica surfaces and is 2 × 10-5 mol/L for carboxyl-bearing surfaces. We also examine the charge regulation with decreasing the cell thickness H below the Debye length -1, where a crossover occurs at the Gouy-Chapman length. In particular, when σm ~ eΓ0 and H ≪ -1, the surface charges remain only partially screened by ions, leading to a nonvanishing electric field in the interior. [ABSTRACT FROM AUTHOR]

We present the first measurement of a bound-state spectrum of the NO-He complex. The recorded spectrum is associated with the first overtone transition of the NO moiety. The IR absorption is detected by exciting the vibrationally excited complex to the Ã-state dissociation continuum. The resulting NO(A) fragment is subsequently ionized in the same laser pulse. We recorded two bands centered around the NO monomer rotational lines, Q11(0.5) and R11(0.5), consistent with an almost free rotation of the NO fragment within the complex. The origin of the spectrum is found at 3724.06 cm-1 blue shifted by 0.21 cm-1 from the corresponding NO monomer origin. The rotational structures of the spectrum are found to be in very good agreement with calculated spectra based on bound states derived from a set of high level ab initio potential energy surfaces [Kłos et al. J. Chem. Phys. 112, 2195 (2000)]. [ABSTRACT FROM AUTHOR]

We present a joint experimental and theoretical study on the high-pressure behavior of bromine confined in the one-dimensional (1D) nanochannels of zeolite AlPO4-5 (AFI) single crystals. Raman scattering experiments indicate that loading bromine into AFI single crystals can lead to the formation of bromine molecular chains inside the nanochannels of the crystals. High-pressure Raman and X-ray diffraction studies demonstrate that high pressure can increase the length of the confined bromine molecular chains and modify the inter- and intramolecular interactions of the molecules. The confined bromine shows a considerably different high-pressure behavior to that of bulk bromine. The pressure-elongated bromine molecular chains can be preserved when the pressure is reduced to ambient pressure. Theoretical simulations explain the experimental results obtained from the Raman spectroscopy and X-ray diffraction studies. Furthermore, we find that the intermolecular distance between confined bromine molecules gradually becomes comparable to the intramolecular bond length in bromine molecules upon compression. This may result in the dissociation of the bromine molecules and the formation of 1D bromine atomic chains at pressures above 24 GPa. Our study suggests that the unique nanoconfinement has a considerable effect on the high-pressure behavior of bromine, and the confined bromine species concomitantly enhance the structural stability of the host AFI single crystals. [ABSTRACT FROM AUTHOR]

A four-component (4c) relativistic state specific multireference coupled cluster (4c-SSMRCC) method has been developed and applied to compute the ground state spectroscopic constants of Ag2, Cu2, Au2, and I2. The reference functions used in these calculations are obtained using computationally inexpensive improved virtual orbital-complete active space configuration interaction scheme. Rigorous size-extensivity and insensitivity towards the intruder state problem make our method an interesting choice for the calculation of the dissociation energy surface. To the best of our knowledge, this study is the first implementation of the SSMRCC within the relativistic framework. The overall agreement of our results, employing the smallest model space, with both theoretical and experimental reference values indicates that the 4c-SSMRCC method can be fruitfully used to describe electronic structures and associated properties of systems containing heavy elements. We observe a relativistic bond stabilization for the coinage metal dimers while the I-I bond is weakened by the relativistic effects. [ABSTRACT FROM AUTHOR]

We present a novel simple model to describe molecular photocells where the energy conversion process takes place by a single molecular donor-acceptor complex attached to electrodes. By applying quantum scattering theory, an open quantum system method, the coherent molecular photocell is described by a wave function. We analyze photon absorption, energy conversion, and quantum yield of a molecular photocell by considering the effects of electron-hole interaction and non-radiative recombination. We model the exciton creation, dissociation, and subsequent effects on quantum yield in the energy domain. We find that depending on the photocell structure, the electron-hole interaction can normally decrease or abnormally increase the cell efficiency. The proposed model helps to understand the mechanisms of molecular photocells, and it can be used to optimize their yield. [ABSTRACT FROM AUTHOR]

In what has been described as the fourth age of quantum chemistry, variational nuclear motion programs are now routinely being used to obtain the vibration-rotation levels and corresponding wavefunctions of small molecules to the sort of high accuracy demanded by comparison with spectroscopy. In this perspective, I will discuss the current state-of-the-art which, for example, shows that these calculations are increasingly competitive with measurements or, indeed, replacing them and thus becoming the primary source of data on key processes. To achieve this accuracy ab initio requires consideration of small effects, routinely ignored in standard calculations, such as those due to quantum electrodynamics. Variational calculations are being used to generate huge lists of transitions which provide the input for models of radiative transport through hot atmospheres and to fill in or even replace measured transition intensities. Future prospects such as the study of molecular states near dissociation, which can provide a link with low-energy chemical reactions, are discussed. [ABSTRACT FROM AUTHOR]

The two-body dissociation reactions of the dication C2H2+2, initiated via double ionization of acetylene molecules by photons in the energy range 31.9-50.0 eV, have been studied by coupling photoelectron-photoion-photoion coincidence and ion imaging techniques. The angular distributions and kinetic energy of product ions, measured in the 31.9-50.0 eV energy range, exhibit significant differences for the three leading dissociation reactions with respect to a previous investigation carried out at a fixed energy of 39.0 eV, providing thus new information on the dynamical evolution of the system. The analysis of the results indicates that such dissociation reactions occur with a different mechanism. In particular, the symmetric dissociation in two CH+ ions is characterized by different dynamics, and the anisotropy of the angular distribution of ionic products increases with photon energy in a more pronounced way than the other two reactions. Moreover, the kinetic energy distribution of the symmetric dissociation reaction exhibits several components that change with photon energy. The new experimental findings cast light on the microscopic evolution of the system and can provide a laboratory reference for new theoretical calculations on specific features of the multidimensional potential energy surface, namely, the structure, energy and symmetry of dication states, the electronic state of dissociation products, energy barriers and their dependence on the geometry of the intermediate state. [ABSTRACT FROM AUTHOR]

A method for calculations of rotational-vibrational states of triatomic molecules up to dissociation threshold (and scattering resonances above it) is devised, that combines hyper-spherical coordinates, sequential diagonalization-truncation procedure, optimized grid DVR, and complex absorbing potential. Efficiency and accuracy of the method and new code are tested by computing the spectrum of ozone up to dissociation threshold, using two different potential energy surfaces. In both cases good agreement with results of previous studies is obtained for the lower energy states localized in the deep (~10 000 cm-1) covalent well. Upper part of the bound state spectrum, within 600 cm-1 below dissociation threshold, is also computed and is analyzed in detail. It is found that long progressions of symmetric-stretching and bending states (up to 8 and 11 quanta, respectively) survive up to dissociation threshold and even above it, whereas excitations of the asymmetric-stretching overtones couple to the local vibration modes, making assignments difficult. Within 140 cm-1 below dissociation threshold, large-amplitude vibrational states of a floppy complex O…O2 are formed over the shallow van derWaals plateau. These are assigned using two local modes: the rocking-motion and the dissociative-motion progressions, up to 6 quanta in each, both with frequency ~20 cm-1. Many of these plateau states are mixed with states of the covalent well. Interestingly, excitation of the rocking-motion helps keeping these states localized within the plateau region, by raising the effective barrier. [ABSTRACT FROM AUTHOR]

The fragmentations of iodine cyanide ions created with 2 to 8 positive charges by photoionization from inner shells with binding energies from 59 eV (I 4d) to ca. 900 eV (I 3p) have been examined by multi-electron and multi-ion coincidence spectroscopy with velocity map imaging ion capability. The charge distributions produced by hole formation in each shell are characterised and systematic effects of the number of charges and of initial charge localisation are found. [ABSTRACT FROM AUTHOR]

Using molecular dynamics simulations of a coarse-grained model of the charged apo-hemoglobin protein complex, this work expands upon our initial report [S. K. Fegan and M. Thachuk, J. Am. Soc. Mass Spectrom. 25, 722-728 (2014)] about control of dissociation channels in the gas phase using specially designed charge tags. Employing a charge hopping algorithm and a range of temperatures, a variety of dissociation channels are found for activated gas-phase protein complexes. At low temperatures, a single monomer unfolds and becomes charge enriched. At higher temperatures, two additional channels open: (i) two monomers unfold and charge enrich and (ii) two monomers compete for unfolding with one eventually dominating and the other reattaching to the complex. At even higher temperatures, other more complex dissociation channels open with three or more monomers competing for unfolding. A model charge tag with five sites is specially designed to either attract or exclude charges. By attaching this tag to the N-terminus of specific monomers, the unfolding of those monomers can be decidedly enhanced or suppressed. In other words, using charge tags to direct the motion of charges in a protein complex provides a mechanism for controlling dissociation. This technique could be used in mass spectrometry experiments to direct forces at specific attachment points in a protein complex, and hence increase the diversity of product channels available for quantitative analysis. In turn, this could provide insight into the function of the protein complex in its native biological environment. From a dynamics perspective, this system provides an interesting example of cooperative behaviour involving motions with differing time scales. [ABSTRACT FROM AUTHOR]

Adsorption and dissociation of hydrocarbons on metallic surfaces represent crucial steps on the path to carburization, eventually leading to dusting corrosion. While adsorption of CO molecules on Fe surface is a barrier-less exothermic process, this is not the case for the dissociation of CO into C and O adatoms and the diffusion of C beneath the surface that are found to be associated with large energy barriers. In practice, these barriers can be affected by numerous factors that combine to favour the CO-Fe reaction such as the abundance of CO and other hydrocarbons as well as the presence of structural defects. From a numerical point of view, studying these factors is challenging and a step-by-step approach is necessary to assess, in particular, the influence of the finite box size on the reaction parameters for adsorption and dissociation of CO on metal surfaces. Here, we use density functional theory (DFT) total energy calculations with the climbing-image nudged elastic band method to estimate the adsorption energies and dissociation barriers for different CO coverages with surface supercells of different sizes. We further compute the effect of periodic boundary condition for DFT calculations and find that the contribution from van der Waals interaction in the computation of adsorption parameters is important as they contribute to correcting the finite-size error in small systems. The dissociation process involves carbon insertion into the Fe surface causing a lattice deformation that requires a larger surface system for unrestricted relaxation. We show that, in the larger surface systems associated with dilute CO-coverages, C-insertion is energetically more favourable, leading to a significant decrease in the dissociation barrier. This observation suggests that a large surface system with dilute coverage is necessary for all similar metal-hydrocarbon reactions in order to study their fundamental electronic mechanisms, as an isolated phenomenon, free from finite-size effects. [ABSTRACT FROM AUTHOR]

Adsorption and dissociation of gaseous carbon monoxide (CO) on metal surfaces is one of the most frequently occurring processes of carburisation, known as primary initiator of metal dusting corrosion. Among the various factors that can significantly influence the carburisation process are the intrinsic surface defects such as single surface vacancies occurring at high concentrations due to their low formation energy. Intuitively, adsorption and dissociation barriers of CO are expected to be lowered in the vicinity of a surface vacancy, due to the strong attractive interaction between the vacancy and the C atom. Here the adsorption energies and dissociation pathways of CO on clean and defective Fe 110 surface are explored by means of density functional theory. Interestingly, we find that the O adatom, resulting from the CO dissociation, is unstable in the electron-deficit neighbourhood of the vacancy due to its large electron affinity, and raises the barrier of the carburisation pathway. Still, a full comparative study between the clean surface and the vacancydefected surface reveals that the complete process of carburisation, starting from adsorption to subsurface diffusion of C, is more favourable in the vicinity of a vacancy defect. [ABSTRACT FROM AUTHOR]

Resonantly enhanced multiphoton ionization via the EF¹Σg+, v' = 6 double-well state has been used to probe the energy region below the third dissociation limit of H2 where several high vibrational levels of the 4¹Σu+ state are expected. Theoretical ab initio potential energy curves for this state predict a deep inner well and shallow outer well where vibrational levels above v = 8 are expected to exhibit the double-well character of the state. Since the 4¹Σu+ state has f -state character, transitions to it from the ground state are nominally forbidden. However, the d character of the outer well of the EF1S+ g state allows access to this state. We report observations of transitions to the v = 9-12 levels of the 4¹Σu+ state and compare their energies to predicted energies calculated from an ab initio potential energy curve with adiabatic corrections. Assignments are based on measured energies and linewidths, rotational constants, and expected transition strengths. The amount of agreement between the predicted values and the observations is mixed, with the largest discrepancies arising for the v = 9 level, owing to strong nonadiabatic electronic mixing in this energy region. [ABSTRACT FROM AUTHOR]

Due to the importance of both static and dynamical correlation in the bond formation, lowdimensional beryllium systems constitute interesting case studies to test correlation methods. Aiming to describe the whole dissociation curve of extended Be systems we chose to apply the method of increments (MoI) in its multireference (MR) formalism. To gain insight into the main characteristics of the wave function, we started by focusing on the description of small Be chains using standard quantum chemical methods. In a next step we applied the MoI to larger beryllium systems, starting from the Be6 ring. The complete active space formalism was employed and the results were used as reference for local MR calculations of the whole dissociation curve. Although this is a wellestablished approach for systems with limited multireference character, its application regarding the description of whole dissociation curves requires further testing. Subsequent to the discussion of the role of the basis set, the method was finally applied to larger rings and extrapolated to an infinite chain. [ABSTRACT FROM AUTHOR]

Resonantly enhanced multiphoton ionization via the EF¹S+g, U' = 6 double-well state has been used to probe the energy region below the third dissociation limit of H2 where several high vibrationallevels of the 4¹S+u state are expected. Theoretical ab initio potential energy curves for this state predict a deep inner well and shallow outer well where vibrational levels above u = 8 are expected to exhibit the double-well character of the state. Since the 4¹S+u state has f-state character, transitions to it from the ground state are nominally forbidden. However, the d character of the outer well of the EF¹S+g state allows access to this state. We report observations of transitions to the u = 9-12 levels of the 4¹S+u state and compare their energies to predicted energies calculated from an ab initio potential energy curve with adiabatic corrections. Assignments are based on measured energies and linewidths, rotational constants, and expected transition strengths. The amount of agreement between the predicted values and the observations is mixed, with the largest discrepancies arising for the u = 9 level, owing to strong nonadiabatic electronic mixing in this energy region. [ABSTRACT FROM AUTHOR]

Resonantly enhanced multiphoton ionization via the EF¹Σg+, v' = 6 double-well state has been used to probe the energy region below the third dissociation limit of H2 where several high vibrational levels of the 4¹Σu+ state are expected. Theoretical ab initio potential energy curves for this state predict a deep inner well and shallow outer well where vibrational levels above v = 8 are expected to exhibit the double-well character of the state. Since the 4¹Σu+ state has f -state character, transitions to it from the ground state are nominally forbidden. However, the d character of the outer well of the EF1S+ g state allows access to this state. We report observations of transitions to the v = 9-12 levels of the 4¹Σu+ state and compare their energies to predicted energies calculated from an ab initio potential energy curve with adiabatic corrections. Assignments are based on measured energies and linewidths, rotational constants, and expected transition strengths. The amount of agreement between the predicted values and the observations is mixed, with the largest discrepancies arising for the v = 9 level, owing to strong nonadiabatic electronic mixing in this energy region. [ABSTRACT FROM AUTHOR]

Resonantly enhanced multiphoton ionization via the EF¹S+g, U' = 6 double-well state has been used to probe the energy region below the third dissociation limit of H2 where several high vibrationallevels of the 4¹S+u state are expected. Theoretical ab initio potential energy curves for this state predict a deep inner well and shallow outer well where vibrational levels above u = 8 are expected to exhibit the double-well character of the state. Since the 4¹S+u state has f-state character, transitions to it from the ground state are nominally forbidden. However, the d character of the outer well of the EF¹S+g state allows access to this state. We report observations of transitions to the u = 9-12 levels of the 4¹S+u state and compare their energies to predicted energies calculated from an ab initio potential energy curve with adiabatic corrections. Assignments are based on measured energies and linewidths, rotational constants, and expected transition strengths. The amount of agreement between the predicted values and the observations is mixed, with the largest discrepancies arising for the u = 9 level, owing to strong nonadiabatic electronic mixing in this energy region. [ABSTRACT FROM AUTHOR]

Accurately modeling surface temperature and surface motion effects is necessary to study moleculesurface reactions in which the energy dissipation to surface phonons can largely affect the observables of interest. We present here a critical comparison of two methods that allow to model such effects, namely, the ab initio molecular dynamics (AIMD) method and the generalized Langevin oscillator (GLO) model, using the dissociation of N2 on W(110) as a benchmark. AIMD is highly accurate as the surface atoms are explicitly part of the dynamics, but this advantage comes with a large computational cost. The GLO model is much more computationally convenient, but accounts for lattice motion effects in a very approximate way. Results show that, despite its simplicity, the GLO model is able to capture the physics of the system to a large extent, returning dissociation probabilities which are in better agreement with AIMD than static-surface results. Furthermore, the GLO model and the AIMD method predict very similar energy transfer to the lattice degrees of freedom in the non-reactive events, and similar dissociation dynamics. [ABSTRACT FROM AUTHOR]

Near-edge X-ray absorption fine-structure (NEXAFS) spectra measured at the C, N, and O Kedges for three molecules containing the amide moiety, N-methylformamide (HCONHCH3), N,Ndimethylformamide (HCON(CH3)2), and N,N-dimethylacetamide (CH3CON(CH3)2) are presented. These molecules have similar structures and differ by the number of methyl groups located at the molecular ends. The fragmentation of these molecules after resonant excitation at different K-edge resonances is also investigated, using a 3D-ion imaging time-of-flight spectrometer. A comparison between the molecules with respect to the relative contributions of the fragments created upon excitation at distinct resonances reveals site-specific fragmentation. Further information about the character of the core-excitation and dissociation process is obtained from the angular distributions of the ion fragments. [ABSTRACT FROM AUTHOR]

Many commercial heterogeneous catalysts are complex structures that contain metal active sites promoted by multiple additives. Developing fundamental understanding about the impact of these perturbations on the local surface reactivity is crucial for catalyst development and optimization. In this contribution, we develop a general framework for identifying underlying mechanisms that control the changes in the surface reactivity of a metal site (more specifically the adsorbate-surface interactions) upon a perturbation in the local environment. This framework allows us to interpret fairly complex interactions on metal surfaces in terms of specific, physically transparent contributions that can be evaluated independently of each other. We use Cs-promoted dissociation of O2 as an example to illustrate our approach. We concluded that the Cs adsorbate affects the outcome of the chemical reaction through a strong alkali-induced electric field interacting with the static dipole moment of the O2/Ag(111) system. [ABSTRACT FROM AUTHOR]

This paper discusses the exciton dissociation process at the donor-acceptor interface in organic photocells. In our previous study, we introduced a local temperature to handle the hot chargetransfer (CT) state and calculated the exciton dissociation probability based on the 1D organic semiconductor model [T. Shimazaki and T. Nakajima, Phys. Chem. Chem. Phys. 17, 12538 (2015)]. Although the hot CT state plays an essential role in exciton dissociations, the probabilities calculated are not high enough to efficiently separate bound electron-hole pairs. This paper focuses on the dimensional (entropy) effect together with the hot CT state effect and shows that cooperative behavior between both effects can improve the exciton dissociation process. In addition, we discuss cooperative effects with site-disorders and external-electric-fields. [ABSTRACT FROM AUTHOR]

The abrupt onset of predissociation in the congested electronic spectra of jet-cooled VC, VN, and VS has been observed using resonant two-photon ionization spectroscopy. It is argued that because of the high density of electronic states in these molecules, the predissociation threshold occurs at the thermochemical threshold for the production of separated atoms in their ground electronic states. As a result, the measured threshold represents the bond dissociation energy. Using this method, bond dissociation energies of D0(VC) = 4.1086(25) eV, D0(VN) = 4.9968(20) eV, and D0(VS) = 4.5353(25) eV are obtained. From these values, enthalpies of formation are derived as Δf,0KH°(VC(g)) = 827.0 ± 8 kJ mol-1, Δf,0KH°(VN(g)) = 500.9 ± 8 kJ mol-1, and Δf,0KH°(VS(g)) = 349.3 ± 8 kJ mol-1. Using a thermochemical cycle and the well-known ionization energies of V, VC, and VN, our results also provide D0(V+-C) = 3.7242(25) eV and D0(V+-N) = 4.6871(20) eV. These values are compared to previous measurements and to computational results. The precision of these bond dissociation energies makes them good candidates for testing computational chemistry methods, particularly those that employ density functional theory. [ABSTRACT FROM AUTHOR]

We measured equilibrium constants for H3O+(H2O)n-1 + H2O ↔ H3O+(H2O)n (n = 4-9) reactions taking place in an ion drift tube with various applied electric fields at gas temperatures of 238-330 K. The zero-field reaction equilibrium constants were determined by extrapolation of those obtained at non-zero electric fields. From the zero-field reaction equilibrium constants, the standard enthalpy and entropy changes, ΔH0n,n-1 and ΔS0n,n-1, of stepwise association for n = 4-8 were derived and were in reasonable agreement with those measured in previous studies. We also examined the electric field dependence of the reaction equilibrium constants at non-zero electric fields for n = 4-8. An effective temperature for the reaction equilibrium constants at non-zero electric field was empirically obtained using a parameter describing the electric field dependence of the reaction equilibrium constants. Furthermore, the size dependence of the parameter was thought to reflect the evolution of the hydrogen-bond structure of H3O+(H2O)n with the cluster size. The reflection of structural information in the electric field dependence of the reaction equilibria is particularly noteworthy. [ABSTRACT FROM AUTHOR]

Structural and magnetic properties of many transition-metal dimers embedded in a defected hexagonal boron nitride monolayer are investigated through density functional calculations to search for systems with magnetic anisotropy energies (MAEs) larger than 30meV. In particular, Ir-Ir@Dh-BN is found to have both large MAE (~126 meV) and high structural stability against dissociation and diffusion, and it hence can serve as magnetic unit in spintronics and quantum computing devices. This giant MAE mainly results from the spin orbit coupling and the magnetization of the upper Ir atom, which is in a rather isolated environment. [ABSTRACT FROM AUTHOR]

We used the explicitly correlated variant of the coupled clusters method with single, double, and noniterative triple excitations [CCSD(T)-F12] to compute two-dimensional potential energy surfaces of van der Waals complexes formed by rare gas atoms (Rg) and NO+(X¹S+) cations. We used the correlation-consistent, triple-zeta (cc-pVTZ-F12) atomic basis sets, and for Kr and Xe rare gases, we employed corresponding pseudopotential cc-pVTZ-PP-F12 atomic basis sets. These basis sets were additionally augmented with mid-bond functions. The complexes are all of skewed T-shape type with Rg atom being closer to the N-side. Using analytical representation of the potentials, we have estimated zero-point energy corrected dissociation energies from anharmonic calculations with BOUND program and also from the harmonic approximation. The binding energies increase with the polarization of the Rg atom in series from He to Xe and are 196 cm-1, 360 cm-1, 1024 cm-1, 1434 cm-1, and 2141 cm-1, respectively. Their corresponding dissociation energies are 132 cm-1, 300 cm-1, 927 cm-1, 1320 cm-1, and 1994 cm-1 for the complexes with He to Xe, respectively. We find good agreement with previous theoretical and experimental results. The harmonic vibrational frequencies were calculated for the bending and stretching modes of the Rg-NO+ complexes. [ABSTRACT FROM AUTHOR]

We analyze the role of the spin-orbit (SO) coupling in the dissociative dynamics of excited alkali atoms at the surface of small rare gas clusters. The electronic structure of the whole system is deduced from a one-electron model based on core polarization pseudo-potentials. It allows us to obtain in the same footing the energy, forces, and non-adiabatic couplings used to simulate the dynamics by means of a surface hopping method. The fine structure state population is analyzed by considering the relative magnitude of the SO coupling ξ, with respect to the spin-free potential energy. We identify three regimes of ξ-values leading to different evolution of adiabatic state population after excitation of the system in the uppermost state of the lowest np ²P shell. For sufficiently small ξ, the final population of the J = 1/2 atomic states, P1/2, grows up linearly from P1/2= 1/3 at ξ = 0 after a diabatic dynamics. For large values of ξ, we observe a rather adiabatic dynamics with P1/2decreasing as ξ increases. For intermediate values of ξ, the coupling is extremely efficient and a complete transfer of population is observed for the set of parameters associated to NaAr3 and NaAr4 clusters. [ABSTRACT FROM AUTHOR]

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH4 dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v3 and 2v3, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v1 symmetric stretch of CH4 is more effective at promoting the dissociative chemisorption of CH4 than exciting the 1v3 antisymmetric stretch. This behavior is explained in terms of symmetry, mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v3 state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. Our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies. [ABSTRACT FROM AUTHOR]

Understanding the mechanism of the interaction of lithium ion conductors with water is crucial for both fundamental and technological points of view. Despite the generally accepted fact that water is one of main sources of the degradation of Li-ion recharge batteries, the physicochemical processes occurring at the water-lithium ion conductor interface are not fully understood. By using synchrotron X-ray photoelectron spectroscopy (SXPS) and O K- and Co L-X-ray absorption near edge structure (XANES), we evidence that H2O is dissociatively adsorbed on LiCoO2 thin film at room temperature resulting in the formation of OH groups and the accumulation of the negative charge at the surface accompanied by electron transfer to the initial empty Co3d (e*g) state. By considering the experimentally obtained energy diagram of the ionic conductor and water, direct charge transfer is not favorable due to a high difference in the chemical potential of the ionic conductor and electronic levels of the molecule. Here, we develop the model for the dissociative water adsorption which explains the electron transfer to LiCoO2 by using the atomistic approach. The model takes into account the intrinsic defects found on the surface (<2 nm depth) by using the depth resolved photoemission experiments and can be explored to other layered transition metal oxides to interpret the interaction of water with the surface of ionic conductors. [ABSTRACT FROM AUTHOR]

Detailed analysis of interactions between all 0+g, 1u, and 0-u weakly bound states of iodine molecule correlating with the I(²P1/2) + I(²P1/2) (bb) dissociation limit has been performed. For this purpose, the 0-u (bb) state has been described using analysis of rotationally resolved excitation spectra of luminescence from the g0-g state populated in a three-step three-color perturbation facilitated excitation scheme via the 0-u state. Energies of 41 rovibrational levels, molecular constants, and potential energy curve have been determined. Energy gaps between closest rovibrational levels of the 0-u and 0+g, 1u (bb) states are found to be large, ~6 cm-1. However, interaction of all three 0+g, 1u, and 0-u (bb) states has been observed. It has been found that the 0-u and 1u electronic states are mixed by heterogeneous interactions, while their mixing with the 0+g one is due to hyperfine interactions predominantly. Admixture coefficients and electronic matrix elements of the coupling between the 0+g ~1u, 0+g ~0-u, and 0-u ~1u states have been estimated. [ABSTRACT FROM AUTHOR]

Quasi-classical trajectory (QCT) calculations are used to study state-specific ro-vibrational energy exchange and dissociation in the O2 + O system. Atom-diatom collisions with energy between 0.1 and 20 eV are calculated with a double many body expansion potential energy surface by Varandas and Pais [Mol. Phys. 65, 843 (1988)]. Inelastic collisions favor mono-quantum vibrational transitions at translational energies above 1.3 eV although multi-quantum transitions are also important. Post-collision vibrational favoring decreases first exponentially and then linearly as Δv increases. Vibrationally elastic collisions (Δv = 0) favor small ΔJ transitions while vibrationally inelastic collisions have equilibrium post-collision rotational distributions. Dissociation exhibits both vibrational and rotational favoring. New vibrational-translational (VT), vibrational-rotational-translational (VRT) energy exchange, and dissociation models are developed based on QCT observations and maximum entropy considerations. Full set of parameters for state-to-state modeling of oxygen is presented. The VT energy exchange model describes 22 000 state-to-state vibrational cross sections using 11 parameters and reproduces vibrational relaxation rates within 30% in the 2500.20 000 K temperature range. The VRT model captures 80 × 106 state-to-state ro-vibrational cross sections using 19 parameters and reproduces vibrational relaxation rates within 60% in the 5000.15 000 K temperature range. The developed dissociation model reproduces state-specific and equilibrium dissociation rates within 25% using just 48 parameters. The maximum entropy framework makes it feasible to upscale ab initio simulation to full nonequilibrium flow calculations. [ABSTRACT FROM AUTHOR]

The adsorption and dissociation of water on mackinawite (layered FeS) surfaces were studied using dispersion-corrected density functional theory (DFT-D2) calculations. The catalytically active sites for H2O and its dissociated products on the FeS {001}, {011}, {100}, and {111} surfaces were determined, and the reaction energetics and kinetics of water dissociation were calculated using the climbing image nudged elastic band technique. Water and its dissociation products are shown to adsorb more strongly onto the least stable FeS{111} surface, which presents low-coordinated cations in the surface, and weakest onto the most stable FeS{001} surface. The adsorption energies decrease in the order FeS{111} > FeS{100} > FeS{011} > FeS{001}. Consistent with the superior reactivity of the FeS{111} surface towards water and its dissociation products, our calculated thermochemical energies and activation barriers suggest that the water dissociation reaction will take place preferentially on the FeS nanoparticle surface with the {111} orientation. These findings improve our understanding of how the different FeS surface structures and the relative stabilities dictate their reactivity towards water adsorption and dissociation. [ABSTRACT FROM AUTHOR]

The quantum dynamics of water dissociative chemisorption on the rigid Ni(111) surface is investigated using a recently developed nine-dimensional potential energy surface. The quantum dynamical model includes explicitly seven degrees of freedom of D2O at fixed surface sites, and the final results were obtained with a site-averaging model. The mode specificity in the site-specific results is reported and analyzed. Finally, the approximate sticking probabilities for various vibrationally excited states of D2O are obtained considering surface lattice effects and formally all nine degrees of freedom. The comparison with experiment reveals the inaccuracy of the density functional theory and suggests the need to improve the potential energy surface. [ABSTRACT FROM AUTHOR]