OH Frequency Research Articles

Facile synthesis of nitrogen-containing multiwalled carbon nanotubes as a worth metal-free electrocatalyst for hydrogen evolution reaction and semicarbazide oxidation

Studies of metal-free carbon nanostructures prove effective in energy and environmental applications due to their molecular tunability and vast chemical space. Herein, we synthesize nitrogen-containing multi-walled carbon nanotubes (N-MWCNTs) via. acid-catalysed incorporation of 3, 4-diaminopyridine into multi-walled carbon nanotubes (MWCNTs), and demonstrating their efficacy in electrocatalytic hydrogen evolution reaction (HER) and semicarbazide (SCB) oxidation for energy and environmental waste management, respectively. Successful synthesis is further confirmed by analysis techniques, i.e. Fourier transform infrared (FTIR) spectral analysis shows the diminishing OH frequency around 3250 cm−1 in MWCNTs after functionalization and the formation of an OC–NH bond in N-MWCNTs at 1710 cm−1. X-ray diffraction (XRD) confirms the incorporation of N-species, while Raman spectroscopic analysis indicates an increase in the ID/IG ratio MWCNTs (∼1) to N-MWCNTs (∼1.25), suggesting more defective sites in the N-MWCNTs nanocomposite. X-ray photoelectron spectroscopy (XPS) reveals peaks at 399.38, 400.49, and 402.05 eV, attributed to pyridinic-N, aromatic amide-N, and protonated amine groups, respectively. N₂ adsorption-desorption studies shows a high Brunauer-Emmett-Teller (BET) surface area for N-MWCNTs (119.22 m2/g) compared to MWCNTs (74.94 m2/g). Linear sweep voltammetry (LSV) profiles demonstrate enhanced activity of N-MWCNTs for both HER and SCB oxidation at an ultralow potential of E = −0.55 V vs RHE at 10 mA/cm2, with a lower Tafel slope of 108 mV.dec−1. Moreover, the electrochemical sensing studies indicates on N-MWCNTs were demonstrating an efficient electron transfer to SCB with the lower detection limit of 0.004 μmol. This work provides carbon-based metal-free electrocatalysts for energy harvesting and environmental management.

Do Electrostatics Control the Diffusive Dynamics of Solitary Water? NMR and MD Studies of Water Translation and Rotation in Dipolar and Ionic Solvents.

NMR-based measurements of the diffusion coefficients and rotation times of solitary water and benzene at 300 K are reported in a diverse collection of 13 conventional organic solvents and 10 imidazolium ionic liquids. Proton chemical shifts of water are found to be correlated to water OH-stretching frequencies, confirming the importance of electrostatic interactions in these shifts. However, the influence of magnetic interactions in aromatic solvents renders chemical shifts a less reliable indicator of electrostatics. Diffusion coefficients (DB) and rotational correlation times (τB) of benzene in the solvents examined are accurately described as functions of viscosity (η) by DB ∝ η-0.81 and τB ∝ η0.64. Literature values of DB and τB in alkane and normal alcohols, which were not included among the solvents studied here, are systematically faster than predicted by these correlations, indicating that factors beyond solvent viscosity play a role in determining the friction on benzene. In contrast to benzene, water diffusion and rotation are poorly described in terms of viscosity alone, even in the dipolar and ionic solvents measured here. The present data and the substantial literature data already available on dilute water diffusion show a systematic dependence of DW on solvent polarity among isoviscous solvents. The aspect of solvent polarity most relevant to water dynamics is the ability of a solvent to accept hydrogen bonds from water, as conveniently quantified by the frequency of water's OH stretching band, ΔνOH. The friction on translation, ζtr = kBT/DW, and rotation, ζrot = kBTτW, are both well correlated by functions of the form ζ(η, ΔνOH) = a1ηa2 exp (a3ΔνOH), where the ai are adjustable parameters. Molecular dynamics simulations reveal a strong coupling between electrostatic and nonelectrostatic water-solvent interactions, which makes it impossible to dissect the friction on water into additive dielectric and hydrodynamic components. Simulations also provide a tentative explanation for the unusual form of the correlating function ζ(η, ΔνOH), at least in the case of ζrot.

What do far-infrared spectra of solitary water in "water-in-solvent" systems reveal about water's solvation and dynamics?

Classical molecular dynamics simulations of water in ionic and dipolar solvents were used to interpret the far-infrared (FIR) rotation/libration spectra of "solitary water" in terms of water's rotational dynamics and interactions with solvents. Seven solvents represented by nonpolarizable all-atom force fields and a series of idealized variable-charge solvents were used to span the range of solvent polarities (hydrogen bonding) studied experimentally. Simulated spectra capture the solvent dependence observed, as well as the relationship between the frequencies of water libration (νL) and OH stretching bands (νOH). In more strongly interacting solvents, simulated νL are ∼20% higher than those of experiment. In all solvents, the simulated spectra are composites of rotational motions about the two axes perpendicular to water's dipole moment, and the different frequencies of these two motions are responsible for the breadth of the libration band and the bimodal shape observed in halide ionic liquids. Simulations overestimate the separation of these two components in most solvents. The character of water rotational motions changes markedly with solvent polarity, from quasi-free rotation in nonpolar and weakly polar solvents to highly constrained libration in strongly hydrogen bonding environments. The changeover to librational motions dominating the spectrum occurs between solvents such as benzene (νL ∼ 250cm-1) and acetonitrile (νL ∼ 400cm-1). For solvents in the latter category, the mean frequency of the experimental FIR band provides a direct measure of mean-squared torques and, therefore, force constants associated with interactions constraining water's librational motion.

Character of the OH Bend-Stretch Combination Band in the Vibrational Spectra of the "Magic" Number H3O+(H2O)20 and D3O+(D2O)20 Cluster Ions.

The fundamental transitions that contribute to the diffuse OH stretching spectrum of water are known to increase in width and intensity with increasing red shift from the free OH frequency. In contrast, the profile of the higher-energy combination band involving the OH stretching and the intramolecular HOH bending modes displays a qualitatively different spectral shape with a much faster falloff on the lower-energy side. We elucidate the molecular origin of this difference by analyzing the shapes of the combination bands in the IR spectra of cryogenically cooled H3O+(H2O)20 and D3O+(D2O)20 clusters. The difference in the shapes of the bands is traced to differences in the dependence of their transition dipole matrix elements on the hydrogen-bonding environment. The fact that individual transitions across the combination band envelope have similar intensities makes it a useful way to determine the participation of various sites in extended H-bonding networks.

The analysis of the BAS OH band in zeolites

The zeolite frameworks ( FER , TON , CHA , and IFR ) with a large diversity of the IR band shapes in the OH stretching region were investigated by combined use of FT-IR spectroscopy and DFT calculations. The analysis of various isolated Brønsted acid sites was performed with a model based on Boltzmann weighted relative energies and OH frequencies obtained by the ω/r correlation method. This approach has recently been used to reveal the non-statistical incorporation of aluminum into the H- MOR framework. The model correctly predicts the band shapes of H- FER and H- TON zeolites in the free OH region of the FT-IR spectra. For H-C HA and H- IFR , however, the mutual BAS interactions cannot be ignored even for high Si/Al ratios, which renders the concept of isolated BAS inadequate. Thus, the periodic calculations of adsorption and catalytic properties of zeotype frameworks should always be carried out with extended models mimicking real heteroatom distribution in these materials. • FER , TON , CHA , and IFR high-silica zeolites with a large diversity of the OH band shapes were investigated. • A combined use of FT-IR spectroscopy and periodic DFT calculations provided rationalization of observed spectral features. • Analysis of 44 different BAS in zeolites was carried out with the ω/r correlation method. • The statistical model of the BAS OH band in high-silica H- CHA was proposed based on empirical FF simulations. • Two mechanisms for the formation of free OH BAS in IFR were identified by analysis of 20 Al pairs at the DFT level.

OH Stretching and Libration Bands of Solitary Water in Ionic Liquids and Dipolar Solvents Share a Single Dependence on Solvent Polarity.

Ionic liquids are an emerging class of materials which are finding application in a variety of technologically important areas. Because of their hydrophilic character, at least a small concentration of water is often present when ionic liquids are used in practical applications. This study employs infrared spectroscopy in the OH stretching and libration regions together with DFT calculations to better characterize the state of dilute water in ionic liquids. Water mole fractions (xw ∼ 0.1) are chosen such that nearly all water occurs in monomeric form and spectra probe the solvation structure and dynamics of solitary water molecules. New data are reported for a series of 1-ethyl-3-methylimidazolium liquids [Im21][X] with X- = (C2F5)3F3P-, (CF3SO2)2N-, BF4-, B(CN)4-, CF3SO3-, C2H5SO4-, NO3-, SCN-, and CH3CO2-, as well as for the two 1-hexyl-3-methylimidazolium liquids [Im61][Cl] and [Im61][I]. For comparison, spectra are also recorded in a variety of dipolar solvents, and much of the available literature data are summarized, providing a comprehensive perspective on monomeric water in homogeneous solution. Most prior studies of dilute water in ionic liquids interpreted OH stretching spectra only in terms of water being specifically bonded to two anions in A-···H-O-H···A- type solvates. The more detailed analysis presented here indicates the additional presence of asymmetrically solvated water, which in some cases includes both singly solvated (A-···H-O-H) and more subtle forms of asymmetric solvation. The same pattern of solvation also pertains to dipolar solvents capable of accepting hydrogen bonds from water. No clear distinction is found between OH spectra in high-polarity conventional solvents and ionic liquids. In all solvents, OH frequencies are strongly correlated to measures of solvent basicity or hydrogen bond accepting ability. Far-infrared spectra of the water libration band also show common trends in ionic and dipolar solvents. Despite the different character of the libration and OH modes, the frequencies of these vibrations show virtually the same solvent dependence (apart from sign) except in weakly polar or nonpolar solvents.

ANALYSIS OF AMBULATORY BLOOD PRESSURE MONITORING AND BLOOD PRESSURE MANAGEMENT IN A GERIATRIC REHABILITATION UNIT

Objective: Blood pressure variability (BPV) has proven prognostic importance. Research has shown that controlling BPV in addition to overall reduction of BP in hypertension improves cardiovascular risk. Patients with diagnosed hypertension have an increased association with wider BPVs. Ambulatory blood pressure monitoring (ABPM) is the gold standard in diagnosis of HTN and measuring BPV. We aimed to analyse ABPM data on rehabilitation inpatients and assess hypertension (HTN) management. Design and method: A retrospective analysis of ABPM data of 32 patients sequentially admitted to a geriatric rehabilitation unit in an orthopaedic hospital from Jan 2019 – Jan 2020. We measured the change in medication, quantifying it by escalation and de-escalation (addition/reduction in antihypertensives) or no change if nothing was done. In addition we measured OH. We also analysed BPV by subdividing patients into three groups – High, Medium, and Low daytime BPV based on the standard deviation of daytime SBP. Results: Patient demographics summary (Table 1). There was increased OH detected in the High variability compared to the Low group this had borderline significance (High 75% vs Low 29%, P – 0.06). 37.5% of patients on anti-HTN treatment had an average SBP > 140mmHg. 66.6% of patients with an average SBP > 140mmHg had postural hypotension. 34% of the cohort had OH. 44% of patients with an SBP > 140mmHg had no previous diagnosis of HTN. In this cohort 87% were non night-time dippers. Increased frequency of OH detected in the High variability compared to the Low. (High 75% vs Low 29%, P – 0.06). The High variability also had a significantly higher eGFR when compared to the Low variability (High 88 vs Low 60, P – 0.04) (Table 2). Conclusions: These results show that a significant sub-group of rehabilitation inpatients in our unit had inadequate blood pressure control, underdiagnosed HTN/BPV. This study has shown that ABPM is an effective method for detecting PBV, HTN and sustained night-time HTN in a geriatric rehab population. ABPM should be used as standard of care to detect BPV and OH so that labile BP can be effectively treated and falls risk reduced.

Looking at the Distant Universe with the MeerKAT Array: Discovery of a Luminous OH Megamaser at z > 0.5

In the local universe, OH megamasers (OHMs) are detected almost exclusively in infrared-luminous galaxies, with a prevalence that increases with IR luminosity, suggesting that they trace gas-rich galaxy mergers. Given the proximity of the rest frequencies of OH and the hyperfine transition of neutral atomic hydrogen (H i), radio surveys to probe the cosmic evolution of H i in galaxies also offer exciting prospects for exploiting OHMs to probe the cosmic history of gas-rich mergers. Using observations for the Looking At the Distant Universe with the MeerKAT Array (LADUMA) deep H i survey, we report the first untargeted detection of an OHM at z > 0.5, LADUMA J033046.20−275518.1 (nicknamed “Nkalakatha”). The host system, WISEA J033046.26−275518.3, is an infrared-luminous radio galaxy whose optical redshift z ≈ 0.52 confirms the MeerKAT emission-line detection as OH at a redshift z OH = 0.5225 ± 0.0001 rather than H i at lower redshift. The detected spectral line has 18.4σ peak significance, a width of 459 ± 59 km s−1, and an integrated luminosity of (6.31 ± 0.18 [statistical] ± 0.31 [systematic]) × 103 L ⊙, placing it among the most luminous OHMs known. The galaxy’s far-infrared luminosity L FIR = (1.576 ±0.013) × 1012 L ⊙ marks it as an ultraluminous infrared galaxy; its ratio of OH and infrared luminosities is similar to those for lower-redshift OHMs. A comparison between optical and OH redshifts offers a slight indication of an OH outflow. This detection represents the first step toward a systematic exploitation of OHMs as a tracer of galaxy growth at high redshifts.

Transfer learned potential energy surfaces: accurate anharmonic vibrational dynamics and dissociation energies for the formic acid monomer and dimer.

The vibrational dynamics of the formic acid monomer (FAM) and dimer (FAD) is investigated from machine-learned potential energy surfaces at the MP2 (PESMP2) and transfer-learned (PESTL) to the CCSD(T) levels of theory. The normal mode (MAEs of 17.6 and 25.1 cm−1) and second order vibrational perturbation theory (VPT2, MAEs of 6.7 and 17.1 cm−1) frequencies from PESTL for all modes below 2000 cm−1 for FAM and FAD agree favourably with experiment. For the OH stretch mode the experimental frequencies are overestimated by more than 150 cm−1 for both FAM and FAD from normal mode calculations. Conversely, VPT2 calculations on PESTL for FAM reproduce the experimental OH frequency to within 22 cm−1. For FAD the VPT2 calculations find the high-frequency OH stretch at 3011 cm−1, compared with an experimentally reported, broad (∼100 cm−1) absorption band with center frequency estimated at ∼3050 cm−1. In agreement with earlier reports, MD simulations at higher temperature shift the position of the OH-stretch in FAM to the red, consistent with improved sampling of the anharmonic regions of the PES. However, for FAD the OH-stretch shifts to the blue and for temperatures higher than 1000 K the dimer partly or fully dissociates using PESTL. Including zero-point energy corrections from diffusion Monte Carlo simulations for FAM and FAD and corrections due to basis set superposition and completeness errors yields a dissociation energy of D0 = −14.23 ± 0.08 kcal mol−1 compared with an experimentally determined value of −14.22 ± 0.12 kcal mol−1.

Isolating the Contributions of Specific Network Sites to the Diffuse Vibrational Spectrum of Interfacial Water with Isotopomer-Selective Spectroscopy of Cold Clusters.

Decoding the structural information contained in the interfacial vibrational spectrum of water requires understanding how the spectral signatures of individual water molecules respond to their local hydrogen bonding environments. In this study, we isolated the contributions for the five classes of sites that differ according to the number of donor (D) and acceptor (A) hydrogen bonds that characterize each site. These patterns were measured by exploiting the unique properties of the water cluster cage structures formed in the gas phase upon hydration of a series of cations M+·(H2O)n (M = Li, Na, Cs, NH4, CH3NH3, H3O, and n = 5, 20-22). This selection of ions was chosen to systematically express the A, AD, AAD, ADD, and AADD hydrogen bonding motifs. The spectral signatures of each site were measured using two-color, IR-IR isotopomer-selective photofragmentation vibrational spectroscopy of the cryogenically cooled, mass selected cluster ions in which a single intact H2O is introduced without isotopic scrambling, an important advantage afforded by the cluster regime. The resulting patterns provide an unprecedented picture of the intrinsic line shapes and spectral complexities associated with excitation of the individual OH groups, as well as the correlation between the frequencies of the two OH groups on the same water molecule, as a function of network site. The properties of the surrounding water network that govern this frequency map are evaluated by dissecting electronic structure calculations that explore how changes in the nearby network structures, both within and beyond the first hydration shell, affect the local frequency of an OH oscillator. The qualitative trends are recovered with a simple model that correlates the OH frequency with the network-modulated local electron density in the center of the OH bond.

Mapping the temperature-dependent and network site-specific onset of spectral diffusion at the surface of a water cluster cage

We explore the kinetic processes that sustain equilibrium in a microscopic, finite system. This is accomplished by monitoring the spontaneous, time-dependent frequency evolution (the frequency autocorrelation) of a single OH oscillator, embedded in a water cluster held in a temperature-controlled ion trap. The measurements are carried out by applying two-color, infrared-infrared photodissociation mass spectrometry to the D3O+·(HDO)(D2O)19 isotopologue of the "magic number" protonated water cluster, H+·(H2O)21 The OH group can occupy any one of the five spectroscopically distinct sites in the distorted pentagonal dodecahedron cage structure. The OH frequency is observed to evolve over tens of milliseconds in the temperature range (90 to 120 K). Starting at 100 K, large "jumps" are observed between two OH frequencies separated by ∼300 cm-1, indicating migration of the OH group from the bound OH site at 3,350 cm-1 to the free position at 3,686 cm-1 Increasing the temperature to 110 K leads to partial interconversion among many sites. All sites are observed to interconvert at 120 K such that the distribution of the unique OH group among them adopts the form one would expect for a canonical ensemble. The spectral dynamics displayed by the clusters thus offer an unprecedented view into the molecular-level processes that drive spectral diffusion in an extended network of water molecules.

A comprehensive infrared spectroscopic and theoretical study on phenol-ethyldimethylsilane dihydrogen-bonded clusters in the S0 and S1 states.

To investigate microscopic characters of Si-H⋯H-O type dihydrogen bonds, we observed OH and SiH stretch bands in both the S0 and S1 states of phenol-ethyldimethylsilane (PhOH-EDMS) clusters by infrared (IR)-ultraviolet (UV) and UV-IR double resonance spectroscopies. Density functional theory (DFT) calculations and energy decomposition analysis were also performed. Structures of two isomers identified were unambiguously determined through the analysis of IR spectra and DFT calculations. To discuss the strength of dihydrogen bond in various systems, we performed theoretical calculations on clusters of EDMS with several acidic molecules in addition to PhOH. It was revealed that charge-transfer interaction energies from a bonding σ orbital of SiH bond to an anti-bonding σ* orbital of OH bond well reflect strengths of dihydrogen bonds. Additionally, it was found that the red shift of SiH stretch frequencies can be used as a crude measure of the strength of dihydrogen bonds. Relationship between the red shifts of OH/SiH stretch frequencies and various electrostatic components of the interaction energy was examined. In the S1 state, large increases in red shifts were observed for both the OH and SiH stretch frequencies. Since the EDMS moiety is not associated with the electronic excitation in a cluster, the strength of dihydrogen bonds in the S1 and S0 states was able to be directly compared based on the red shifts of the SiH stretch bands. A significant increase in the red shift of SiH stretch frequency indicates a strengthening of the dihydrogen bonds during the electronic excitation of the PhOH moiety.

Temperature and Nuclear Quantum Effects on the Stretching Modes of the Water Hexamer.

The water hexamer has many low-lying isomers, e.g., ring, book, cage, and prism, shifting from two- to three-dimensional structures. We show that this dimensionality change is accompanied by a drop in the quantum nature of the cluster, as manifested in the red shift of the quantal OH stretching modes as compared with their classical counterparts. We obtain this “nuclear quantum effect” (NQE) as the mean deviation between the OH stretch frequencies from velocity autocorrelation Fourier transforms from classical trajectories on a high-level water potential (MB-pol) as compared with scaled harmonic frequencies from high-level quantum chemistry calculations. With a universal scaling factor, the predicted OH frequencies agree with experiment to a mean absolute deviation ≤10 cm–1, which allows unequivocal isomer assignments. By assuming temperature-independent NQEs, we produce the temperature dependence of the cage isomer OH stretch spectrum below 70 K, where it is the dominant structure. All bands widen and blue-shift with increasing temperature, most conspicuously the reddest mode, which thus constitutes a “vibrational thermometer”.

Competitive Selection of Hydroxylamine on Ammonia Oxidizing Bacteria and Nitrite Oxidizing Bacteria

The effective inhibition of nitrite oxidizing bacteria (NOB) is the key to realizing satisfactory nitrite accumulation and achieving effective nitritation. In order to explore the selective effect of hydroxylamine (NH2 OH) on ammonia oxidizing bacteria (AOB) and NOB, a sequencing batch reactor (SBR) with the operation mode of anaerobic/aerobic/anoxia (A/O/A) was used to observe the start-up of nitritation at different concentrations and frequencies of NH2 OH. The results showed that when 5 mg·L-1 of NH2 OH was added once every 2 cycles, the nitrite accumulation rate (NAR) increased from 0.1% to 57.4% in 6 days, and was maintained at (62.0±4.6)% until the end of the trials. In the typical cycle on day 6, the NN4+-N dropped from 26.05 mg·L-1 to 8.06 mg·L-1, thus producing 9.02 mg·L-1 of NO2--N and 6.70 mg·L-1 of NO3--N. Meanwhile, the ratio of the maximum activity of AOB (rAOB) to NOB (rNOB) increased from 1.05 on day 1 to 4.22 on day 9. Moreover, qPCR results indicated that the abundance of AOB and NOB decreased to 30.2% and 19.1%, respectively, on day 9 in comparison to the original sample. The results indicate that the selective effect of AOB and NOB based on NH2 OH is expected to provide a feasible application for the rapid start-up nitritation of municipal wastewater.

Solubility of hydroxyl groups in pyroxenes: Effect of oxygen fugacity at 0.2–3 GPa and 800–1200 °C

Clinopyroxene and orthopyroxene are important constituents of the upper mantle, and determine largely the water budget. Despite considerable efforts on water storage in pyroxenes, however, less attention has been paid to the effect of oxygen fugacity, a key thermodynamic factor in Earth sciences. We have systematically assessed the effect of oxygen fugacity on OH dissolution in pyroxenes, by conducting high-pressure and temperature experiments over a wide range of conditions. The runs were carried out at 0.2–3 GPa, 800–1200 °C and peridotite- and H2O-saturated conditions, with gem-quality natural diopside and enstatite single crystals and a fresh peridotite xenolith as the starting materials. The oxygen fugacities were buffered by Fe-FeO, Ni-NiO, Re-ReO2 and Fe3O4-Fe2O3 pairs, by using a modified double-capsule technique. The water contents of the recovered pyroxenes were determined by polarized analyses with a Fourier-transform infrared spectroscopy.The H-annealed pyroxenes show typical OH-related bands. The samples show no zoned OH distribution at sub-grain scales, and the OH contents are independent of run durations, suggesting the attainments of equilibrium OH incorporation. For each starting mineral, the spectral shapes and OH frequency positions are similar throughout the run conditions. The measured H2O contents are ∼14–394 and 34–227 ppm in the H-annealed clinopyroxene and orthopyroxene, respectively. For each mineral under otherwise identical conditions, the OH content increases with increasing pressure or temperature but decreases with increasing oxygen fugacity. In clinopyroxene, the ratio of either the peak heights or integrated absorbances between the bands at ∼3645 and 3435 cm−1 is less sensitive to a change of pressure, particularly above 1 GPa, but is more sensitive to a change of temperature, if the redox state is maintained as in the upper mantle. The OH groups in the spectra of clinopyroxene can be used to estimate the redox state in the source regions where the sample was finally equilibrated, if the equilibrium temperature is determined by other approach(s). On average, the OH content is enhanced by ∼40% and 60% in Fe-poor clinopyroxene and orthopyroxene, respectively, at Fe-FeO buffered reducing than at Ni-NiO buffered oxidizing conditions. This enhancement appears greater if the pyroxenes are more Fe-enriched, likely due to the enhanced reduction of Fe3+ to Fe2+ and the coupled incorporation of H in the structure toward more reducing conditions. The quantitative dependence of OH solubility on oxygen fugacity differs between pyroxenes and olivine (and other nominally anhydrous minerals), and the partitioning of OH between pyroxenes and coexisting olivine and the inventory of OH in the upper mantle are influenced by oxygen fugacity. The OH storage capacity of the shallow mantle is probably greater in Mars than in the Earth, because of the relatively more reduced state and more Fe-enriched pyroxenes in the former. Finally, the enhanced solubility of OH in pyroxenes under very reducing conditions could be important for insights into the early differentiation of Earth’s shallow mantle, in that hydrous melting may have been induced by redox-involved dehydration of pyroxenes when the shallow mantle evolved into its modern oxidizing state.

Coupling of three intramolecular vibration modes of liquid H2O molecules in the framework of the fluctuation theory of hydrogen bonding.

Vibrational spectra of liquid water contain a wealth of information about its structure and dynamics but there are no generally acknowledged interpretation of their band profiles, unfortunately. We have tried to calculate them taking into account only the coupling of three intramolecular vibrations in the set of H2O molecules with different initial oscillator frequencies and intensities. The matter is that each water molecule forms hydrogen bonds of different strengths; thus the OH stretching band spans several hundreds of wave numbers (the fluctuation theory of hydrogen bonding). This distribution overlaps with the similar band of the first overtone of the HOH bending frequencies thus triggering a Fermi resonance between three vibrations. There were some problems causing some simplifications in previous theoretical modeling of vibrational transitions in condensed water. To solve them we extract the statistical distribution of OH frequencies of H2O molecules directly from the experimental spectra of HOD molecules at the same conditions instead of defining it theoretically. Also the bending overtone is allowed to have non-zero intrinsic intensity when calculating the Fermi resonance. The test calculation of the isotropic component of the Raman spectrum which is most critical for interpretation shows that our algorithm can reproduces the characteristic peculiarities of the experiment. The spectrum consists of three non-Gaussian contours. The overtone of bending vibration, being strengthened by Fermi resonance, makes the greatest contribution to the dominating low-frequency spectrum component that was previously attributed to intermolecular coupling of adjacent OH oscillators by some authors. Further we plan to calculate similar band profiles in the IR and also Raman isotropic and anisotropic spectra of Н2О and D2О molecules within a wide temperature range for their quantitative comparison with experiment.

Hydrogen bonding effect on Raman modes of Formic acid-water binary solutions

Raman spectroscopy in combination with density functional theory (DFT) calculation was used to investigate the interaction between water and Formic acid. Raman spectra of formic acid (FA)-water binary solutions with different concentrations had been obtained at room temperature and ambient pressure. Gaussian deconvolution analysis was used for explaining the effect of FA on the OH stretching band. The frequencies of symmetric and asymmetric OH stretching mode changed significantly when the volume fraction of FA is 0.2 and 0.8 respectively, which attributed to the hydrogen bonding (HB) structure of water was affected, leading to FA-water structure undergo two phase transitions. Besides, the Raman frequencies of CO and CH stretching mode of FA also reverse at both two concentrations, which represent the main species of FA molecules were transformed. These results about the transition of FA-water structure and formic-formic acid structure were analyzed theoretically through Raman spectra and compared with the concrete details from density functional theory (B3LYP) calculations with 6-311++G(d, p) level.

Aqueous hydroxyl group as the vibrational probe to access the hydrophobicity of amide derivatives

First principles molecular dynamics (FPMD) simulations of relatively dilute aqueous solutions of N-methylformamide (NMF), N, N-dimethylacetamide (DMA), N-methylacetamide (NMA) were carried out to elucidate the effects of variation of hydrophobicity of amide molecules on structure, dynamics and spectral properties of solvating water molecules. A quantitative analysis of dangling OH groups of water molecules, one of the consequences of hydrophobicity, around the amide molecules was performed to explore the structure of surrounding water molecules. We observe that DMA has the most hydrophobic character among the three amide molecules; the lifetime of dangling OH mode of water molecules and the number of such modes are found to be more inside the solvation shell of DMA as compared to NMA and NMF molecules. Overall this lifetime is more inside the solvation shell of amides compared to the bulk water molecules for all aqueous solutions of amides. Rotational dynamics calculation suggests significant retardation of OH bonds of water near the amide oxygen atom (O) due to the OwHw⋯O strong hydrogen bonds. A moderate slowdown of reorientational dynamics is also observed for OH modes that are close to the hydrophobic surface of DMA in its aqueous solution. Vibrational density of states (VDOS) and frequency distribution calculations point out the higher average stretching frequency (~3600–3850 cm−1) of free OH groups. Hydrogen bond lifetime calculations conceive that DMA, having three methyl groups, makes stronger hydrogen bonds through the CO moiety. Vibrational spectral diffusion of bulk water and solvation shell water molecules were also calculated in combination with wavelet transform and frequency-frequency autocorrelation functions. The CO group affected OH stretching frequency bands for aqueous solutions of NMF and NMA molecules are more pronounced than that of DMA. However, NH affected OH frequency bands are less pronounced for NMA and DMA due to the presence of more number of hydrophobic methyl groups. Going from NMF to DMA, the OH frequency bands inside the amide solvation shells shift towards the higher value due to the enhancement of hydrophobicity. The vibrational spectral diffusion of OH modes around CO and NH (N for DMA) groups, as well as for bulk water molecules, is also investigated. Three time scales were found for these calculations for all the cases. The fast time scales in the range ~50–100 fs are due to the amide-water intact hydrogen bonding, and two slower time scales in the range ~0.6–3.90 ps and ~10–20 ps were found. The time scales in the range of ~0.6 to 3.90 ps can be attributed to carbonyl-water and N-H-water hydrogen bonding, and the very long time scales are due to the escape dynamics water molecules from the solvation shell of CO and NH (N for DMA) groups.

Disentangling the Complex Vibrational Mechanics of the Protonated Water Trimer by Rational Control of Its Hydrogen Bonds

The vibrational spectrum of the protonated water trimer, H+(H2O)3, is surprisingly complex, with many strong features in the expected region of the fundamentals associated with two H-bonded OH groups on the H3O+ core ion. Here we follow how the bands in this region of the spectrum evolve when the energies of the fundamentals in the H-bonded OH stretches are systematically increased by the attachment of increasingly strongly bound "tag" molecules (He, Ar, D2, N2, CO, and H2O) to the free OH position on the hydronium core ion of H+(H2O)3, as well as by replacement of the hydrogen atom in the nonbonded OH group on hydronium with methyl and ethyl groups. This allows for the incremental transformation of the complex band pattern observed in H+(H2O)3 into that of the "Eigen" structure of the protonated water tetramer. Differences among the trajectories of the various bands provide an empirical way to disentangle features primarily due to the displacements of the OH stretches bound to the hydronium core from those arising from anharmonic coupling to states involving one or more quanta in lower frequency modes. The latter are found to be dramatically enhanced when the nominal frequencies of the intermolecular OH stretching modes approach those of the intramolecular bends of the H3O+ and H2O constituents in both H and D isotopologues.

Effects of complexation with a metal ion on the intramolecular hydrogen bonds in acylphloroglucinols

Complexation with a metal ion of an organic molecule containing one or more intramolecular hydrogen bonds (IHBs) influences the characteristics of the IHBs. These influences are here investigated computationally for the complexes of selected antioxidant acylphloroglucinols with a Cu2+ ion, and also the complexes of a number of structurally-related molecules meant to highlight the influence of specific molecular features. All the low energy conformers of acylphloroglucinols (compounds structurally derived from 1,3,5-trihydroxybenzene and characterised by the presence of a CRO group) contain an IHB between the sp2 O of CRO and a neighbouring phenol OH. Additional O–H···O or O–H···π IHB are present when the molecule contains substituents with groups that can form IHBs. The results show various effects that can be ascribed to complexation, such as changes in the IHB parameters and in the red shift of the vibrational frequency of the donor OH caused by the IHB. For O–H···O IHBs, complexation may cause the transfer of the proton from the donor to the acceptor O atom, more frequently when the acceptor is an sp2 O (i.e. for stronger IHBs). In some cases, IHBs that are not present in the uncomplexed conformers appear in the complex. The type and extent of the changes depend mainly on the site/s to which the Cu2+ ion binds and, to a less extent, also on the geometry features of the conformer. Some changes offer clear indications of weakening or strengthening of specific IHBs for specific binding sites of the ion.