OH-stretching Modes Research Articles

Water adsorption on the LaMnO3 surface.

Studying the adsorption of water on the metallic LaMnO3 surface can provide insight into this complicated surface-adsorbate interaction. Using density functional theory, we investigated the adsorption of a water monomer, dimer, trimer, and a monolayer on the surface. The electronic structure of ground state configurations is explored using analysis of density of states, charge density, and crystal orbital overlap populations. We found that the interaction between the surface and water molecules is stronger than hydrogen bonding between molecules, which facilitates wetting of the surface. Adsorbed water molecules form very strong hydrogen bonds, with substantially shifted OH stretch modes. For the monolayer of adsorbed water, a hint of a bilayer is observed with a height separation of only 0.2 A. However, simulated scanning tunneling microscopy images and vibrational spectra suggest a significant difference between the two layers due to intermolecular bonding and interaction with the substrate.

Origin of the Hadži ABC structure: An ab initio study.

Medium and strong hydrogen bonds are well known to give rise to broad features in the vibrational spectrum often spanning several hundred wavenumbers. In some cases, these features can span over 1000 cm(-1) and even contain multiple broad peaks. One class of strongly hydrogen-bonded dimers that includes many different phosphinic, phosphoric, sulfinic, and selenic acid homodimers exhibits a three-peaked structure over 1500 cm(-1) broad. This unusual feature is often referred to as the Hadži ABC structure. The origin of this feature has been debated since its discovery in the 1950s. Only a couple of theoretical studies have attempted to interpret the origin of this feature; however, no previous study has been able to reproduce this feature from first principles. Here, we present the first ab initio calculation of the Hadži ABC structure. Using a reduced dimensionality calculation that includes four vibrational modes, we are able to reproduce the three-peak structure and much of the broadness of the feature. Our results indicate that Fermi resonances of the in-plane bend, out-of-plane bend, and combination of these bends play significant roles in explaining this feature. Much of the broadness of the feature and the ability of the OH stretch mode to couple with many overtone bending modes are captured by including an adiabatically separated dimer stretch mode in the model. This mode modulates the distance between the monomer units and accordingly the strength of the hydrogen-bonds causing the OH stretch frequency to shift from 2000 to 3000 cm(-1). Using this model, we were also able to reproduce the vibrational spectrum of the deuterated isotopologue which consists of a single 500 cm(-1) broad feature. Whereas previous empirical studies have asserted that Fermi resonances contribute very little to this feature, our study indicates that while not appearing as a separate peak, a Fermi resonance of the in-plane bend contributes substantially to the feature.

Study of the phase transition in lysozyme crystals by Raman spectroscopy

BackgroundRecently, it has been revealed that tetragonal lysozyme crystals show a phase transition at 307K upon heating. The underlying mechanisms of the phase transition are still not fully understood. Here we focus on the study of high-frequency vibrational modes arising from the protein and their temperature evolution in the vicinity of Tph as well as on the detailed study of crystalline water dynamics near Tph. MethodsRaman experiments have been performed at temperatures 295–323K including Tph. The low-frequency modes and the modes of fingerprint region, CH- and OH-stretching regions have been analyzed. Results and conclusionsIn spite of the absence of noticeable rearrangements in protein structure, the high-frequency vibrational modes of lysozyme located in the fingerprint region have been found to exhibit the features of critical dynamics near Tph. Pronounced changes in the dynamics of α-helixes and Tyr residues exposed on the protein surface point to the important role of H-bond rearrangements at the phase transition. Additionally the study of temperature evolution of OH-stretching modes has shown an increase in distortions of tertahedral H-bond network of crystalline water above Tph. These changes in water dynamics could play a crucial role in the mechanisms of the phase transition. General significanceThe present results shed light on the mechanisms of the phase transition in lysozyme crystals.

Pre-resonance-stimulated Raman scattering for water bilayer structure on laser-induced plasma bubble surface.

Pre-resonance-stimulated Raman scattering (PSRS) from water molecules in the air/water interfacial regions was studied when the laser-induced plasma bubble was generated at the interfaces. A characteristically lower Raman shift of OH-stretching vibrational modes of water molecules at around 3000 cm(-1) (370 meV) was observed, in which the mechanisms were possibly attributed to the strong hydrogen bond in a well-ordered water bilayer structure that was formed on a laser-induced plasma bubble surface. Simultaneously, the PSRS of ice Ih at about 3100 cm(-1) was obtained, which also belonged to the strong hydrogen bond effect in ice Ih structure.

Iron oxide formation from FeCl2 solutions in the presence of uranyl (UO22+) cations and carbonate rich media

The mineral goethite (α-FeOOH) has previously been investigated as a thermodynamically stable repository for many potentially toxic metals (e.g., Cd, Pb, Cu). The substitution of uranium (U as uranyl, UO22+) for Fe, however, has been studied sparingly, and conclusive uranium incorporation into the goethite structure has been obscured by formation of ploymineralic Fe systems that all appeared involved in U’s sequestration. In this study, we investigated the formation of goethite from FeCl2 in the presence of seven nominal uranyl concentrations (0.2–4mole percent, U/(U+Fe)×100) and characterised the solids using quantitative X-ray diffraction (QXRD), X-ray absorption fine structure (XAFS) spectroscopy at the U LIII edge (17,166eV), diffuse reflectance infrared Fourier Transform (DRIFT) spectrometry and congruency of acid dissolution. Our findings show that U does indeed, however sparingly, incorporate into the goethite structure. The unit cell volume, ascertained from Rietveld models of XRD patterns, increased linearly as a function of U content, which could be ascribed to a linear increase of the unit cell length a and c. The highest U-for-Fe substitution was 0.48mole percent, however, most U-containing goethite samples showed substitution levels around 0.2mole percent, which was in good agreement with previous findings. DRIFT spectra showed a shift of the symmetric Fe–O and asymmetric Fe–OH stretch modes (τ–O and τ–OH bands, respectively) to lower frequency, which by Hooks analogy, can only occur if a heavier atom substitutes for Fe, i.e., U. The congruency of acid dissolution results showed that fractional U release was greater than the corresponding fractional Fe release into solution, suggesting that U was overall more soluble. In two of the synthates, however, (initial U mole percent of 2 and 4), the dissolution was congruent. XAFS data collected on a selected subset of samples showed the disappearance of the uranyl moiety with higher levels of U incorporation and acid extraction. In sample S6, non-linear least-square fits of the extended XAFS data demonstrated that the coordination environment around U atoms was sixfold occupied by O/OH atoms and was further coordinated by next nearest Fe neighbours that are 1.063±0.008times inflated in distance to the normal Fe–Fe distances in goethite without U substitution. Despite low levels of incorporation, U bound by goethite was recalcitrant to desorption/dissolution in increasingly acidic solutions thus warranting further research into the possibility of using iron oxides as a sink for U.

Origin of the 900 cm(-1) broad double-hump OH vibrational feature of strongly hydrogen-bonded carboxylic acids.

Medium and strong hydrogen bonds are common in biological systems. Here, they provide structural support and can act as proton transfer relays to drive electron and/or energy transfer. Infrared spectroscopy is a sensitive probe of molecular structure and hydrogen bond strength but strongly hydrogen-bonded structures often exhibit very broad and complex vibrational bands. As an example, strong hydrogen bonds between carboxylic acids and nitrogen-containing aromatic bases commonly display a 900 cm(-1) broad feature with a remarkable double-hump structure. Although previous studies have assigned this feature to the OH, the exact origin of the shape and width of this unusual feature is not well understood. In this study, we present ab initio calculations of the contributions of the OH stretch and bend vibrational modes to the vibrational spectrum of strongly hydrogen-bonded heterodimers of carboxylic acids and nitrogen-containing aromatic bases, taking the 7-azaindole--acetic acid and pyridine--acetic acid dimers as examples. Our calculations take into account coupling between the OH stretch and bend modes as well as how both of these modes are affected by lower frequency dimer stretch modes, which modulate the distance between the monomers. Our calculations reproduce the broadness and the double-hump structure of the OH vibrational feature. Where the spectral broadness is primarily caused by the dimer stretch modes strongly modulating the frequency of the OH stretch mode, the double-hump structure results from a Fermi resonance between the out of the plane OH bend and the OH stretch modes.

Molecular vibrational dynamics in water studied by femtosecond coherent anti-Stokes Raman spectroscopy

We utilized femtosecond time-resolved coherent anti-Stokes Raman spectroscopy (CARS) to study the ultrafast vibrational dynamics in distilled water at room temperature. The CARS signals from the broad OH-stretching modes between 3100cm−1 and 3700cm−1 were obtained and analyzed. The dephasing times of four Raman modes in water were detected and compared.

Competitive reaction pathways in vibrationally induced photodissociation of H2SO4.

Vibrationally induced photodissociation of sulfuric acid into H2O + SO3 is investigated based on reactive molecular dynamics (MD) simulations. Multisurface adiabatic reactive MD simulations allow us to follow both, H-transfer and water elimination after excitation of the ν9 OH-stretching mode. Analysis of several thousand trajectories finds that the H2O and SO3 fragments have distinct final state distributions with respect to translational, rotational, and vibrational degrees of freedom. Rotational distributions peak at quantum numbers j ≤ 5 for water and j ≈ 60 for SO3. The final state distributions should be useful in identifying products in forthcoming experiments. Based on the MD trajectories, a kinetic scheme has been developed which is able to explain most of the trajectory data and suggests that IVR is very rapid. Typical lifetimes of the excited complex range from several 10 picoseconds to hundreds of nanoseconds, depending on the excitation level. Including temperature and pressure profiles characteristic for the stratosphere in the kinetic model shows that excitations higher than ν9 = 4 can significantly contribute to the photolysis rate. This extends and specifies earlier work in that multi-level modeling is required to understand the significance of vibrationally induced decomposition pathways of sulfuric acid in the middle atmosphere.

Correction to “Sub-Doppler Spectroscopy of the trans-HOCO Radical in the OH Stretching Mode”

Correction to “Sub-Doppler Spectroscopy of the <i>trans</i>-HOCO Radical in the OH Stretching Mode”

X-Ray Diffraction and Vibrational Spectroscopic Characteristics of Hydroxylclinohumite from Ruby-Bearing Marbles (Luc Yen District, Vietnam)

A honey-yellow hydroxylclinohumite from ruby-bearing marbles of the Luc Yen district in northern Vietnam was characterized by electron microprobe (EPMA), single-crystal X-ray diffraction (XRD), micro-Raman, and Fourier-transform infrared (FTIR) spectroscopy. The studied crystals correspond to nearly ideal clinohumite with the structural formula 4[Mg2SiO4]·[(Mg,Fe,Ti)(OH,F)2] and roughly equal F and OH proportions. Crystal structure analysis showed Ti substitution for Mg only at the Mg3 site. A Fourier-difference map revealed one hydrogen site associated with ninth oxygen atom. The calculated O–H bond distance was shorter than that in other natural clinohumites. FTIR revealed bands corresponding to combination of OH-stretching with Mg–OH and/or Fe–OH bending modes, combinations of OH−and Fe–OH vibrations, combination of fundamental bands of the Si–OH bonding, combination of OH−and Si–OH vibrations, and first (2νOH) and the second (3νOH) overtones of the OH-stretching vibration mode. Two groups of OH-stretching vibration and FTIR absorption bands at 3390–3420 cm−1and 3560–3580 cm−1show reversible temperature-dependent shift. The low-frequency bands absent in pure synthetic hydroxylclinohumites are assigned to OH-planar defects caused by Ti-for-Mg substitution.

Vibrational Dynamics of Interfacial Water by Free Induction Decay Sum Frequency Generation (FID-SFG) at the Al2O3(1120)/H2O Interface.

The dephasing dynamics of a vibrational coherence may reveal the interactions of chemical functional groups with their environment. To investigate this process at a surface, we employ free induction decay sum frequency generation (FID-SFG) to measure the time that it takes for free OH stretch oscillators at the charged (pH ≈ 13, KOH) interface of alumina/water (Al2O3/H2O) to lose their collective coherence. By employing noncollinear optical parametric amplification (NOPA) technology and nonlinear vibrational spectroscopy, we showed that the single free OH peak actually corresponds to two distinct oscillators oriented opposite to each other and measured the total dephasing time, T2, of the free OH stretch modes at the Al2O3/H2O interface with a sub-40 fs temporal resolution. Our results suggested that the free OH oscillators associated with interfacial water dephase on the time scale of 89.4 ± 6.9 fs, whereas the homogeneous dephasing of interfacial alumina hydroxyls is an order of magnitude slower.

Raman and infrared study of hydroxyl sites in natural uvite, fluor-uvite, magnesio-foitite, dravite and elbaite tourmalines

We present the Raman and infrared spectra of different tourmaline species in the spectral range associated with the hydroxyl stretching modes, investigated through polarized Raman spectroscopy. Different lineshapes are observed for the OH spectra in uvite, fluor-uvite, magnesio-foitite, dravite and elbaite samples, and can be related to the coordination of OH in the two different structural V[O(3)]- and W[O(1)]-occupied sites. Local arrangements around the two different OH sites were assigned, and different ion substitutions for these five tourmaline species were identified. Our work with polarized Raman spectroscopy revealed that OH-stretching modes are described by totally symmetric, irreducible representations.

Direct Pathway for Water–Gas Shift Reaction in Gas Phase

Abstract A direct reaction pathway for water–gas shift reaction (WGSR) in gas phase, H2O + CO → H2 + CO2, was discovered by using anharmonic downward distortion following method. The direct WGSR is accompanied by a roaming-like mechanism. To examine the initial conditions of the direct WGSR, we carried out ab initio molecular dynamics simulations and showed that cooperative excitations of OH-stretching vibrational modes and the orientational control of reactants are required for the direct WGSR.

Contribution of interstitial OH groups to the incorporation of water in forsterite

Water incorporation in forsterite samples synthesized under low to medium silica-activity conditions mostly occurs via a substitutional mechanism in which a Si vacancy is compensated by four protons. Corresponding IR absorption spectra display a cluster of narrow and weakly anharmonic OH-stretching bands at wavenumbers above 3,500 cm−1. However, this diagnostic spectrum is often superimposed to one broader absorption band, rarely two, displaying pronounced temperature-dependent properties and tentatively assigned to H atoms in interstitial position (Ingrin et al. in Phys Chem Miner 40:499–510, 2013). Here, we investigate the structural and vibrational properties of selected interstitial H-bearing defects in forsterite using a first-principles modeling approach. We show that the broad bands discussed by Ingrin et al. (Phys Chem Miner 40:499–510, 2013) are most likely related to interstitial OH groups in the vacant octahedral sites alternating with the M2 sites along the c axis of the forsterite structure. The corresponding OH defects lead to the formation of fivefold coordinated Si species. Their peculiar thermal properties stem from the vibrational phase relaxation due to the anharmonic coupling of the high-energy local OH-stretching mode with a low-energy vibrational mode. This “exchange mode” corresponds to the hindered longitudinal translation of the OH group. These results suggest that at high pressure, hydrogen incorporation in forsterite is dominated by coexisting interstitial OH groups and (4H)Si defects.

The crystal structure of galgenbergite-(Ce), CaCe2(CO3)4∙H2O

Galgenbergite-(Ce) from the type locality, the railroad tunnel Galgenberg between Leoben and St. Michael, Styria, Austria, was investigated. There it occurs in small fissures of an albite-chlorite schist as very thin tabular crystals building rosette-shaped aggregates associated with siderite, ancylite-(Ce), pyrite and calcite. Electron microprobe analyses gave CaO 9.49, Ce2O3 28.95, La2O3 11.70, Nd2O3 11.86, Pr2O3 3.48, CO2 30.00, H2O 3.07, total 98.55 wt.%. CO2 and H2O calculated by stoichiometry. The empirical formula (based on Ca + REE ∑3.0) is \( \mathrm{C}{{\mathrm{a}}_{1.00 }}{{\left( {\mathrm{C}{{\mathrm{e}}_{1.04 }}\mathrm{L}{{\mathrm{a}}_{0.42 }}\mathrm{N}{{\mathrm{d}}_{0.42 }}\mathrm{P}{{\mathrm{r}}_{0.12 }}} \right)}_{2.00 }}{{\left( {\mathrm{C}{{\mathrm{O}}_3}} \right)}_4}\cdot {{\mathrm{H}}_2}\mathrm{O} \), and the simplified formula is \( \mathrm{CaC}{{\mathrm{e}}_2}{{\left( {\mathrm{C}{{\mathrm{O}}_3}} \right)}_4}\cdot {{\mathrm{H}}_2}\mathrm{O} \). According to X-ray single crystal diffraction galgenbergite-(Ce) is triclinic, space group \( P\overline{1},a=6.3916(5) \), b = 6.4005(4), c = 12.3898(9) A, α = 100.884(4), β = 96.525(4), γ = 100.492(4)°, V = 483.64(6) A3, Z = 2. The eight strongest lines in the powder X-ray diffraction pattern are [dcalc in A/(I)/hkl]: 5.052/(100)/011; 3.011/(70)/0-22; 3.006/(66)/004; 5.899/(59)/-101; 3.900/(51)/1-12; 3.125/(46)/-201; 2.526/(42)/022; 4.694/(38)/-102. The infrared absorption spectrum reveals H2O (OH-stretching mode at 3,489 cm−1, HOH bending mode at 1,607 cm−1) and indicates the presence of distinctly non-equivalent CO3-groups by double and quadruple peaks of their ν1, ν2, ν3 and ν4 modes. The crystal structure of galgenbergite-(Ce) was refined with X-ray single crystal data to R1 = 0.019 for 2,448 unique reflections (I > 2σ(I)) and 193 parameters. The three cation sites of the structure Ca(1), Ce(2) and Ce(3) have a modest mixed site occupation by Ca and small amount of REE (Ce, La, Pr, Nd) and vice versa. The structure is based on double layers parallel to (001), which are composed of Ca(1)Ce(2)(CO3)2 single layers with an ordered chessboard like arrangement of Ca and Ce, and with a roof tile-like stacking of the CO3 groups. Perpendicular to (001) the double layers are connected to a triclinic framework structure with good cleavage parallel to (001) by a differently organized and more open part of the structure formed by Ce(3)(CO3)2(H2O). Based on the topology of the CaCe(CO3)2 single layer in galgenbergite-(Ce), structural relationships to rutherfordine, to aragonite and ancylite type minerals, and to lanthanite are outlined.

Atelisite-(Y), a new rare earth defect silicate of the KDP structure type

The title mineral has been discovered in a granitic pegmatite at the Stetind quarry, Tysfjord, Norway. Atelisite-(Y) forms pale brown to colourless, transparent crystals of dipyramidally terminated, short-prismatic habit with a diameter of up to 0.3 mm. Based on electron microprobe analysis and 16 anions per formula unit, the empirical formula is (Y 3.11 Yb 0.46 Er 0.19 Dy 0.11 Gd 0.09 Ho 0.01 Tb 0.02 ) ∑3.99 Si 2.40 O 16 H 10.43 The presence of hydroxyl-groups is inferred from the detection of OH-stretching modes near 3225 cm −1 in Raman spectra of the new mineral. The crystal structure of atelisite was solved and refined on single-crystal X-ray diffraction data in space group I 42 d , with a = 6.947(4), c = 6.133(3) A, V = 295.98(28) A 3 . Site occupancy refinement at the 4a-site approaches 3/4 Si-occupancy, if the 4b-site is fully occupied by Y and Yb, with a refined Y/Yb ratio of 4. This suggests an idealized formula of Y 4 Si 3 O 8 (OH) 8 for atelisite-(Y). The crystal structure of the new mineral is of particular interest with regard to the known occurrence of hydrous species in the nominally anhydrous minerals xenotime and zircon.

Effects of Collisional and Vibrational Velocity on Proton and Deuteron Transfer in the Reaction of HOD+ with CO

Reaction of HOD(+) with CO was studied over the collision energy (E(col)) range between 0.18 and 2.87 eV, for HOD(+) in its ground state and with one quantum in each of its vibrational modes: (001)--predominantly OH stretch; (010)--bend, and (100)--predominately OD stretch. In addition to integral cross sections, product recoil velocity distributions were also measured for each initial condition. The dominant reactions are near-thermoneutral proton and deuteron transfer, generating HCO(+) and DCO(+) product ions by a predominantly direct mechanism. The HCO(+) and DCO(+) channels occur with a combined efficiency of 76% for ground state HOD(+) at our lowest E(col), increasing to 94% for E(col) around 0.33 eV, then falling at high E(col) to ~40%. The HCO(+) and DCO(+) channels have a complicated dependence on the HOD(+) vibrational state. Excitation of the OH or OD stretch modes enhances H(+) or D(+) transfer, respectively, and inhibits D(+) or H(+) transfer. Bend excitation preferentially enhances H(+) transfer, with no effect on D(+) transfer. There is no coupling of energy initially in any HOD(+) vibrational mode to recoil velocity of either of the product ions, even at low E(col) where vibrational excitation doubles or triples the energy available to products. The results suggest that transfer of H or D atoms is enhanced if the atom in question has a high vibrational velocity, and that this effect offsets what is otherwise a general inhibition of reactivity by added energy. HOCO(+) + D and DOCO(+) + H products are also observed, but as minor channels despite being barrierless and exoergic. These channels appear to be complex mediated at low E(col), essentially vanish at intermediate E(col), then reappear with a direct reaction mechanism at high E(col).

Localized thermal mapping using coherent anti-Stokes Raman spectroscopy

Coherent anti-Stokes Raman scattering (CARS) spectroscopy is explored as a tool for obtaining micro-scale thermal measurements. A single femtosecond oscillator is used to pump a photonic crystal fiber to provide the broadband Stokes pulse. The CARS signals from the broad OH-stretching modes between 3000 and 3600 cm(-1) are shown to correlate with temperature with an accuracy of ± 1°C for water and ± 1.5°C for phosphate-buffered saline. Local variation of temperature is mapped on a microscopic level, using black-dyed microspheres as thermal sources.

Hydration structure and dynamics of a hydroxide ion in water clusters of varying size and temperature: Quantum chemical and ab initio molecular dynamics studies

We have investigated the hydration structure and dynamics of OH−(H2O)n clusters (n=4, 8, 16 and 20) by means of quantum chemical and ab initio molecular dynamics calculations. Quantum chemical calculations reveal that the solvation structure of the hydroxide ion transforms from three and four-coordinated surface states to five-coordinated interior state with increase in cluster size. Several other isomeric structures with energies not very different from the most stable isomer are also found. Ab initio simulations show that the most probable configurations at higher temperatures need not be the lowest energy isomeric structure. The rates of proton transfer in these clusters are found to be slower than that in bulk water. The vibrational spectral calculations reveal distinct features for free OH (deuterated) stretch modes of water in different hydrogen bonding states. Effects of temperature on the structural and dynamical properties are also investigated for the largest cluster considered here.

Ultrafast Vibrational Frequency Shifts Induced by Electronic Excitations: Naphthols in Low Dielectric Media

We study the solvent-induced frequency shifts of the OH-stretching mode of 1-naphthol and 2-naphthol in nonpolar/weakly polar solvents, subject to electronic excitation, with ultrafast UV/mid-infrared pump-probe spectroscopy and theoretical modeling based on Pullin's perturbative treatment of vibrational solvatochromic effects. The model is parametrized at the density functional theory (DFT) level, including the B3LYP/TZVP and TD-B3LYP/TZVP descriptions, for the naphthol chromophores in the S(0)- and (1)L(b)-states and accounts for both the static and the optical dielectric response of the solvent on time scales comparable to that of the OH-stretching vibrational motions. The favorable comparison between experimental and theoretical values of the solvent-induced vibrational frequency shifts suggests that the ultrafast dielectric response of the solvent contributes predominantly to the solvatochromic shifts in solvents of moderate polarity where specific solute-solvent interactions are absent.