Hydrogen-bonded Water Molecules Research Articles

Harnessing Nuclear Magnetic Resonance Spectroscopy to Decipher Structure and Dynamics of Clathrate Hydrates in Confinement: A Perspective.

This perspective outlines recent developments in the field of NMR spectroscopy, enabling new opportunities for in situ studies on bulk and confined clathrate hydrates. These hydrates are crystalline ice-like materials, built up from hydrogen-bonded water molecules, forming cages occluding non-polar gaseous guest molecules, including CH4, CO2 and even H2 and He gas. In nature, they are found in low-temperature and high-pressure conditions. Synthetic confined versions hold immense potential for energy storage and transportation, as well as for carbon capture and storage. Using previous studies, this report highlights static and magic angle spinning NMR hardware and strategies enabling the study of clathrate hydrate formation in situ, in bulk and in nano-confinement. The information obtained from such studies includes phase identification, dynamics, gas exchange processes, mechanistic studies and the molecular-level elucidation of the interactions between water, guest molecules and confining interfaces.

Binding energies and hydrogen bonds effects on DNA-cisplatin interactions: a DFT-xTB study.

A systematic study of hydrogen bonds in base pairs and the interaction of cisplatin with DNA fragments was carried out. Structure, binding energies, and electron density were analyzed. xTB has proven to be an accurate method for obtaining structures and binding energies in DNA structures. Our xTB values for DNA base binding energy were in the same order and in some cases better than CAM-B3LYP values compared to experimental values. Double-stranded DNA-cisplatin structures have been calculated and the hydrogen bonds of water molecules are a decisive factor contributing to the preference for the cisplatin-Guanine interaction. Higher values of the water hydrogen bonding energies were obtained in cisplatin-Guanine structures. Furthermore, the electrostatic potential was used to investigate and improve the analysis of DNA-cisplatin structures. We applied the xTB method and the CAM-B3LYP functional combined with def2-SVP basis set to perform and analyze of the bonding energies of the cisplatin interaction and the effects of the hydrogen bonds. Results were calculated employing the xTB and the ORCA software.

Mesomorphology of clathrate hydrates from molecular ordering.

Clathrate hydrates are crystals formed by guest molecules that stabilize cages of hydrogen-bonded water molecules. Whereas thermodynamic equilibrium is well described via the van der Waals and Platteeuw approach, the increasing concerns with global warming and energy transition require extending the knowledge to non-equilibrium conditions in multiphase, sheared systems, in a multiscale framework. Potential macro-applications concern the storage of carbon dioxide in the form of clathrates, and the reduction of hydrate inhibition additives currently required in hydrocarbon production. We evidence porous mesomorphologies as key to bridging the molecular scales to macro-applications of low solubility guests. We discuss the coupling of molecular ordering with the mesoscales, including (i) the emergence of porous patterns as a combined factor from the walk over the free energy landscape and 3D competitive nucleation and growth and (ii) the role of molecular attachment rates in crystallization-diffusion models that allow predicting the timescale of pore sealing. This is a perspective study that discusses the use of discrete models (molecular dynamics) to build continuum models (phase field models, crystallization laws, and transport phenomena) to predict multiscale manifestations at a feasible computational cost. Several advances in correlated fields (ice, polymers, alloys, and nanoparticles) are discussed in the scenario of clathrate hydrates, as well as the challenges and necessary developments to push the field forward.

Unraveling the Hydration Shell Structure and Dynamics of Group 10 Aqua Ions.

We present ab initio simulations based on subsystem DFT of group 10 aqua ions accurately compared against experimental data on hydration structure. Our simulations provide insights into the molecular structures and dynamics of hydration shells, offering recalibrated interpretations of experimental results. We observe a soft, but distinct second hydration shell in Palladium (Pd) due to a balance between thermal fluctuations, metal-water interactions, and hydrogen bonding. Nickel (Ni) and platinum (Pt) exhibit more rigid hydration shells. Notably, our simulations align with experimental findings for Pd, showing axial hydration marked by a broad peak at about 3 Å in the Pd-O radial distribution function, revising the previously sharp "mesoshell" prediction. We introduce the "hydrogen bond dome" concept to describe a resilient network of hydrogen-bonded water molecules around the metal, which plays a critical role in the axial hydration dynamics.

Spectroscopic Characterization of Hydrogen-Bonded 2,7-Diazaindole Water Complex Isolated in the Gas Phase.

We present a systematic experimental analysis of the 1:1 complex of 2,7-diazaindole (27DAI) with water in the gas phase. The complex was characterized by using two-color-resonant two-photon ionization (R2PI), laser-induced fluorescence (LIF), single vibronic level fluorescence (SVLF), and photoionization efficiency (PIE) spectroscopic methods. The 000 band of the S1←S0 electronic transition of the 27DAI-H2O complex was observed at 33,074 cm-1, largely red-shifted by 836 cm-1 compared to that of the bare 27DAI. From the R2PI spectrum, the detected modes at 141 (ν'Tx), 169 (ν'Ty), and 194 (ν'Ry) cm-1 were identified as the internal motions of the H2O molecule in the complex. However, these modes were detected at 115 (ν″Tx), 152 (ν″Ty), and 190 (ν″Ry) cm-1 in the ground state, which suggested a stronger hydrogen bonding interaction in the photo-excited state. The structural determination was aided by the detection of νNH and νOH values in the ground and excited state complexes using the FDIR and IDIR spectroscopies. The detection of νNH at 3414 and νOH at 3447 cm-1 in 27DAI-H2O has shown an excellent correlation with the most stable structure consisting of N(1)-H···O and OH···N(7) hydrogen-bonded bridging water molecule in the ground state. The structure of the complex in the electronic excited state (S1) was confirmed by the corresponding bands at 3210 (νNH) and 3265 cm-1 (νOH). The IR-UV hole-burning spectroscopy confirmed the presence of only one isomer in the molecular beam. The ionization energy (IE) of the 27DAI-H2O complex was obtained as 8.789 ± 0.002 eV, which was significantly higher than the 7AI-H2O complex. The higher IE values of N-rich molecules suggest a higher resistivity of such molecules against photodamage. The obtained structure of the 27DAI-H2O complex has explicitly shown the formation of a cyclic one-solvent bridge incorporating N(1)-H···O and O-H···N(7) hydrogen bonds upon microsolvation. The lower excitation and higher ionization energies of the 27DAI-H2O complex compared to 7AI-H2O established higher stabilization of N-rich molecules. The solvent clusters forming a linear bridge between the hydrogen/proton acceptor and donor sites in the complex can be considered as a stepping stone to investigate the photoinduced deactivation mechanisms in nitrogen containing biologically relevant molecules.

Study on the mechanism of interaction between cations and the surface of nano-SiO2 particle in the salt solution by using molecular dynamics simulation

Nano-SiO2 solution has great potential for application in the field of oil and gas exploration and development. However, its application is restricted due to the aggregation of nano-SiO2 in stratum water. This paper studies the process of interaction between nano-SiO2 particles and salt solutions by using the molecular dynamics simulation experiments, including the characteristics of transportation and diffusion of cations around the nano SiO2, the effect of cations on the recombination and destruction of hydrogen bonds, the interaction energy between cations and nano SiO2. The main results are as follows. During the transportation and diffusion of cations in the solution, the hydrogen bonds of water molecules are broken, so that the hydrogen bonds can be rearranged, and a stable solvated layer can be formed. In the solvated layer, the repulsive force of solvation can prevent the charge exchange between cation and the charged surface of nano SiO2 particle. Compared with the monovalent salt solution, more divalent cations can break through the solvation layer to generate the charge exchange on the surface of nano-SiO2 particle. More divalent cations can conduct small amplitude oscillation movement near the surface of nano-SiO2 particle due to the strong electrostatic effect. When the concentration of salt solution is increased (3000 mg/L → 7000 mg/L) and the valence of cations is increased (monovalent → bivalent), the hydrogen bond is easier to break through the solvation layer to gather on the surface of nano SiO2 particles, which is unfavorable to the stability of nano SiO2 particles. When the cations transport to the position of 7 Å away from the surface of nano-SiO2 particles, the short-range force (including hydrogen bond force, van der Waals force, and electrostatic force) begins to affect the movement of cations. When the cations transport to the position of 2 ∼ 3 Å away from the surface of nano-SiO2 particles, the charge exchange occurs between cations and the surface of nano SiO2 particle, so that the local energy is increased and the cation continues to oscillate. In summary, with the increasing of concentration of salt solution and the valence state, more cations can break through the solvation layer to be adsorbed on the surface of nano SiO2 particle, showing that the ability of transportation and diffusion of cations is weakened, the interaction energy between nano SiO2 particle and salt solution molecules is enhanced. The electrostatic force is the main force to destroy the stability of nano SiO2 particle. The conclusions can provide a certain theoretical basis for the efficient application of nano-SiO2 materials in the field of oil and gas exploration and development and other interrelated industry.

The NaClO4-water eutectic electrolyte for environmentally friendly electrical double-layer capacitors operating at low temperature

Herein, owing to its remarkable ionic conductivity, the 8.84 mol kg−1 NaClO4 water-in-salt (WIS) eutectic electrolyte is suggested for the low temperature operation of electrical double-layer capacitors down to -35 °C. Molecular dynamic simulations reveal that the local structure of the solution remains relatively stable from RT to -35 °C, with distinct channel-like domains formed by hydrogen-bonded water molecules, which facilitate the ionic diffusion within the bulk of the electrolyte. Interestingly, on activated carbon (AC) electrodes, the electrolyte demonstrates an electrochemical stability window (ESW) increasing from 1.8 V to 2.1 V as temperature decreases from 25 °C to -35 °C. The high ESW of this electrolyte is due to i) pH close to neutrality enabling high overpotential of water reduction on porous AC electrodes; ii) WIS characteristics with a reduced amount of free water in the Stern layer under positive polarization of AC; iii) higher oxidation potential at low temperature ascribed to the enhanced immobilization of the ClO4− anions in the Stern layer as well as reduced diffusion of water molecules in the AC electrode porosity. The electrochemical investigations on laminate AC//AC cells in the NaClO4-water electrolyte demonstrate low values of their resistive components down to -30 °C, while the devices can operate with rated voltage of 2.0 V and 1.7 V at -30 °C and RT, respectively. At -30 °C and under discharge power as high as 10 kW kg−1, the AC//AC capacitor in the NaClO4-water electrolyte outperforms the specific output energy of a traditional AC//AC cell in the 1 M TEABF4/ACN electrolyte. Hence, for sub-ambient temperatures, the presented environmentally friendly EDLC holds promise to compete with traditional devices implementing an organic electrolyte.

Ni(II) triggered sensing and reversible uptake of ammonia by tetrazole based Ni(II) metallogel: A one-pot mechanistic approach

The release of ammonia gas and its removal through traditional approaches is a critical challenge inhibiting the sustainability of chemical industries. The quest to improve sustainability has triggered interest to develop chemoprobe and reusable adsorbent for toxic gases such as ammonia. The present study offers the first example of a novel one-pot synthesis of a stable Ni(II)metallogel (Ni(II)MG) from 1, 4 adiponitrile and sodium azide. The Ni(II)MG is composed of Ni(II) coordinated with four in-situ formed CN-Tz (5-(1H-tetrazol-5-yl)pentanenitrile) ligands and two water molecules forming predominant octahedral geometry. The Ni(II)MG has good strength, and viscoelastic, thixotropic, and self-healing properties. The Ni(II)MG and its xerogel (Ni(II)XG) have been thoroughly characterized and utilized for ammonia sensing and reversible adsorption at ambient condition. The mesoporous nature and presence of hydrogen-bonded water molecules in the pores make this material effective for reversible adsorption of ammonia. The lewis acidic Ni(II) increases the cloud network of hydrogen-bonded water molecules and triggers the coordinated water molecules to activate hydrogen-bonded water molecules for binding the ammonia molecules. The Ni(II) triggered extended hydrogen bonding through coordinated water molecule is also supported by DFT studies. The Ni(II)XG shows good ammonia adsorption capacity (8 mmol/gm) which is confirmed by TPD studies. The properties of Ni(II)XG are found to be intact after ammonia adsorption even after 20 cycles. Hence, it could be a promising low cost, sustainable and reusable material as a chemoprobe for removal of ammonia.

Meteorological Data and Spectral Analyses of Non-Equilibrium Processes in Water during the Total Solar Eclipse of 11.08.1999 in Bulgaria

There are partial or total solar eclipses every year on our planet. They are observed from relatively small areas. From 1950 to 2100, three total solar eclipses fell within the territory of Bulgaria. The two solar eclipses from the 20th century were observed on 15.02.1961 and 11.08.1999. The next total solar eclipse will happen on 3.09.2081. The partial solar eclipses in Bulgaria were on 3.10.2005, 29.03.2006, 1.09.2008, 4.01.2011, and 25.10.2022. The question of the influence of solar eclipses on the Earth’s atmosphere, water, and living organisms is an area of interest for many researchers. In this connection, studies have been conducted on atmospheric and water parameters during partial and total solar eclipses. Most investigations were performed with meteorological data – temperature and humidity. In the last 30 years, other methods have also been applied for the investigations of solar eclipses – spectral methods with infrared (IR) spectroscopy, studies of magnetic and electric fields, polarization, and measurements of the parameters of the fluids in plants. Our studies have used meteorological methods and analyses. For the effects on the water, spectral methods are applied to the non-equilibrium energy spectrum (NES) and differential non-equilibrium spectrum (DNES). A deionized water sample examined during the solar eclipse on 11.08.1999 was used, aiming to analyze the parameters of NES and DNES. The deionized water control sample was tested on 10.08.1999 at the same time as the solar eclipse of the next day. The results of our research show relatively rapid and significant changes in air parameters during a solar eclipse, which are most prominent immediately after its culmination. The conditions of non-equilibrium arising during the solar eclipse allow for studying the restructuring of the hydrogen bonds of water molecules. The results of the current studies prove that the solar eclipse’s significantly affect water which is the primary substance in the Nature and living organisms. These data are consistent with other ones which also prove that, during a solar eclipse, the structure of water undergoes significant changes. By influencing the water, this natural phenomenon affects the whole Nature and all living organisms on the planet.

Ethylenediamine modulate bonding interaction of solvation structure for wide-temperature aqueous ammonium-ion capacitor

Aqueous ammonium-ion capacitors (AAICs) are promising for large-scale energy storage owing to low cost and inherent safety, while their practical applications are suffered from performance under extreme environment. Low ion conductivity and high viscosity, as well as freezing of the electrolyte, are the main issues for the electrochemical performance failure at low temperatures. In this work, the AAICs were assembled with commercial carbon electrodes and antifreeze electrolyte, where the electrolyte with a freezing point lower than −115 °C is developed by using Ethylenediamine (EDA) as an additive with a volume ratio of 50 % to an aqueous solution of 0.5 M NH4Cl. This antifreeze electrolyte displays a superior ionic conductivity of 8.58 mS cm−1 and a weaker viscosity of 8.16 mPa s at low temperatures. Furthermore, the spectroscopic investigations and molecular dynamics (MD) simulations demonstrate that the addition of EDA can break the hydrogen bonds of water molecules and modulate the solvation structure. Therefore, the assembled AAICs with electrolytes of 0.5 M NH4Cl (50 %-EDA) could be operated at wide-temperature conditions steadily, exhibiting excellent capacity, rate performance and good cycling stability. This work provides a simple and effective strategy for wide-temperature energy storage devices.

Investigation of encapsulated water wire within self-assembled hydrophilic nanochannels, in a modified γ4-amino acid crystals: Tracking thermally induced changes of intermolecular interactions within a crystalline hydrate

Nanostructures formed by the self-assembly of modified/unmodified amino acids have the potential to be useful in several biological/nonbiological applications. In that regard, the greater conformational space provided by γ-amino acids, owing to their additional backbone torsional degrees of freedom and enhanced proteolytic stability, compared to their α-counterparts, should be explored. Though, modified single amino acid-based nanomaterials such as nanobelts or hydrogels are developed by utilizing the monosubstituted γ-amino acids derived from the backbone homologation of phenylalanine (Phe). Examples of a single γ-amino acid-based porous nanostructure capable of accommodating solvent molecules are not really known. The crystal structures of a modified γ4(R)Phe residue, Boc-γ4(R)Phe-OH, at different temperatures, showed that hydrogen-bonded water molecules are forming a wire inside hydrophilic nanochannels. The dynamics of intermolecular interactions between the water wire and the inner wall of the channel with relation to the temperature change was investigated by analyzing the natural bonding orbital (NBO) calculation results performed with the single crystal structures obtained at different temperature points. The NBO results showed that from 325 K onward, the strength of water–water interactions in the water wire are getting weaker, whereas, for the water–inner wall interactions, it getting stronger, suggesting a favorable change in the orientation of water molecules with temperatures, for the latter.

Phase Transition and Switchable Dielectric Properties of a Three-Dimensional Hydrogen-Bonding Framework Based on Cobalt (Ⅲ), o-Bromoaniline, and 18-Crown-6

The organic–inorganic hybrid compound, (o-BrAH)[H2Co(CN)6]0.5·(18-crown-6)0.5·H2O, was synthesized and characterized by variable-temperature X-ray diffraction, single-crystal diffraction, infrared spectroscopy, elemental analysis, thermogravimetric analysis, differential scanning calorimetry, and dielectric measurements. Single-crystal X-ray diffraction revealed a three-dimensional cage-like structure formed through the hydrogen bonds of cobalt hexacyanide, supermolecular cations, and water molecules. Temperature variation triggered an abrupt change in the cage structure and simultaneously caused dynamic oscillation of the supramolecules within the framework of [Co(CN)6]3−, inducing a phase transition accompanied by a step-like change in the dielectric physical properties.

Effects of sodium chloride on mechanical properties in amorphous polymers of waterlogged archaeological wood: Insights from molecular dynamics simulations

Sodium chloride (NaCl) is the main soluble salt component of marine waterlogged archaeological wood, and it causes deterioration of wood fibres. In this study, a molecular dynamics simulation of three types of archaeological wood from the Quanzhou Song Shipwreck was employed to investigate the impact of NaCl on the mechanical properties of amorphous components consisting of amorphous cellulose, hemicellulose, and lignin. The findings revealed that water molecules bound to the fibres enhanced the mechanical performance of the woody fibres. However, NaCl affected the stability and mechanical properties of the amorphous components. By using molecular dynamics simulations, 24 sets of amorphous fibre models, consisting of fir, pine, and camphorwood with salt concentrations ranging from 0 % to 7 %, were constructed to further analyse the influence of salt content on the mechanical properties of the amorphous components. The results showed that all three species of archaeological wood exhibited similar trends, with the adsorption energy and radial distribution function between wood fibres and water molecules decreasing with increasing NaCl concentration, leading to the gradual rupture of hydrogen bonds in water molecules. Consequently, more water molecules engage in ion hydration, resulting in an increase in the amount of free water within the amorphous regions. This, in turn, degrades the mechanical properties of the amorphous components. This study contributes significantly to a comprehensive understanding of the mechanical properties of marine archaeological wood and is important for decision-making in studies related to the preservation and evaluation of marine waterlogged wooden artefacts.

Water is a radiation protection agent for ionised pyrrole.

Radiation-induced damage of biological matter is an ubiquitous problem in nature. The influence of the hydration environment is widely discussed, but its exact role remains elusive. Utilising well defined solvated-molecule aggregates, we experimentally observed a hydrogen-bonded water molecule acting as a radiation protection agent for ionised pyrrole, a prototypical aromatic biomolecule. Pure samples of pyrrole and pyrrole(H2O) were outer-valence ionised and the subsequent damage and relaxation processes were studied. Bare pyrrole ions fragmented through the breaking of C-C or N-C covalent bonds. However, for pyrrole(H2O)+, we observed a strong protection of the pyrrole ring through the dissociative release of neutral water or by transferring an electron or proton across the hydrogen bond. Overall, a single water molecule strongly reduces the fragmentation probability and thus the persistent radiation damage of singly-ionised pyrrole.

Probing Dielectric Relaxation of Water at Electrochemical Interfaces with Low-Frequency SERS Spectroscopy

Dynamic and structural properties of hydrogen-bonded water molecules in liquid phase have a significant impact on many chemical and biological processes in aqueous systems. Therefore, the bulk behavior of water is quite actively studied from both experimental and theoretical point of view. In the frequency domain, collective motions of water molecules appear in the terahertz (THz) range. For example, the central frequency of Debye-type dielectric relaxation of water exists at around 1 cm-1, and that of the so-called fast Debye relaxation is found at around 10 cm-1. There are several spectroscopic means to obtain such low-frequency information in the bulk liquid of water. However, for interfacial water molecules interacting with a solid surface, their dynamic behavior of hydrogen-bond networks remains unexplored in the experimental research field, despite of the importance of such behavior to molecular-level understanding of heterogeneous electrochemical processes. The reason for lack of such information is due to lack of adequate surface-selective spectroscopic means. In this talk, in-situ observation of the relaxational and vibrational dynamics of water at electrochemical interfaces is demonstrated using low-frequency surface-enhanced Raman spectroscopy (SERS). In this spectroscopic method, not only intermolecular dynamics but also intramolecular vibrational behaviors of water can be simultaneously monitored due to the intrinsic nature of the inelastic scattering technique accessible in the wide frequency range covering both THz and mid-IR regions, which helps us to understand the relation between microscopic and macroscopic behaviors of water molecules.To obtain low-frequency SERS spectrum, volume Bragg grating filters were used for both monochromatization of He-Ne laser radiation of 632.8 nm and removal of Rayleigh scattered light [1]. SERS-active Au electrodes were prepared by electrochemical surface roughening of Au surface in 0.1M KCl solution. For SERS-active Pt electrodes, monoatomic Pt overlayers were formed on the roughened Au surfaces. SERS spectra for interfacial water were measured on these electrode surfaces under application of electrochemical potentials. The measured spectra were converted to density states of formats by reducing the Purcell factor, Bose-Einstein thermal factor, and frequency factor, which can unveil vibrational features in low-frequency range [2-5].The measured spectra clearly showed potential-dependent features in the THz region. According to the previously reported spectra for bulk water, these features were assigned to the fast Debye relaxation component and two intermolecular vibration modes of interfacial water layer. By analyzing the observed spectral features by the assistance of classical molecular dynamics (MD) simulations, we found that the potential-induced change of water orientation causes formation of local defects in hydrogen-bonded networks of interfacial water layer and the lateral mobility of such defects on negatively charged surface is larger than that on positively charged surface [6]. Figure shows the dynamical behavior of potential-induced defects in hydrogen-bonded networks of interfacial water molecules on negatively and positively charge surfaces. The details will be discussed in the presentation.[1] M. Inagaki, K. Motobayashi, K. Ikeda, J. Phys. Chem. Lett., 8, 4236-4240 (2017).[2] M. Inagaki, T. Isogai, K. Motobayashi, K. -Q. Lin, B. Ren, K. Ikeda, Chem. Sci., 11, 9807-9717 (2020).[3] M. Inagaki, K. Motobayashi, K. Ikeda, Nanoscale, 12, 22988-22994 (2020).[4] R. Kamimura, T. Kondo, K. Motobayashi, K. Ikeda, Phys. Status Solidi B, 259, 2100589 (2022).[5] T. Kondo, M. Inagaki, K. Motobayashi, K. Ikeda, Catal. Sci. Technol., 12, 2670-2676 (2022).[6] T. Isogai, M. Inagaki, M. Uranagase, K. Motobayashi, S. Ogata, K. Ikeda, submitted. Figure 1

Magnetization coupled reverse osmosis (RO): Enhanced inhibition scaling mechanisms and operation optimization

In this study, magnetization pretreatment was applied to the reverse osmosis process. The scale inhibition effect and the mechanism of magnetization treatment were analyzed. The results show that after magnetization, the decay of water flux tended to slow down during RO and the flux recovery increased after cleaning. The Ryznar stability index of the solutions was calculated, which showed that magnetization could increase the solubility of carbonate solution and reduce the trend of carbonate scaling to a certain extent. The infrared spectra of the solutions showed that the hydrogen bonds of water molecules in the solution decreased after magnetization, indicating that the magnetization made the hydrogen bonds of water molecules break to form smaller clusters of water molecules, which might make the water molecules pass through the membrane more easily. After magnetization, the crystal size of the carbonate precipitated decreased and the sedimentation rate slowed down. Different flow rates and magnetization times were selected during the magnetization process. The results showed that when the flow velocity was greater than 0.24 m/s, the RSI, scale size and precipitation rate of the magnetized solution changed significantly compared with that of the unmagnetized solution. At the flow velocity of 0.48 m/s, the optimal magnetization time is 5 min. Moreover, the SEM characterization of the fouled membrane after filtration showed that after magnetization, the calcium carbonate deposited on the membrane surface appeared aragonite crystal, and the fouling was more loose, so it was easier to wash away during the membrane cleaning process.

First-Principles Approach for Coupled Quantum Dynamics of Electrons and Protons in Heterogeneous Systems.

The coupled quantum dynamics of electrons and protons is ubiquitous in many dynamical processes involving light-matter interaction, such as solar energy conversion in chemical systems and photosynthesis. A first-principles description of such nuclear-electronic quantum dynamics requires not only the time-dependent treatment of nonequilibrium electron dynamics but also that of quantum protons. Quantum mechanical correlation between electrons and protons adds further complexity to such coupled dynamics. Here we extend real-time nuclear-electronic orbital time-dependent density functional theory (RT-NEO-TDDFT) to periodic systems and perform first-principles simulations of coupled quantum dynamics of electrons and protons in complex heterogeneous systems. The process studied is an electronically excited-state intramolecular proton transfer of o-hydroxybenzaldehyde in water and at a silicon (111) semiconductor-molecule interface. These simulations illustrate how environments such as hydrogen-bonding water molecules and an extended material surface impact the dynamical process on the atomistic level. Depending on how the molecule is chemisorbed on the surface, excited-state electron transfer from the molecule to the semiconductor surface can inhibit ultrafast proton transfer within the molecule. This Letter elucidates how heterogeneous environments influence the balance between the quantum mechanical proton transfer and excited electron dynamics. The periodic RT-NEO-TDDFT approach is applicable to a wide range of other photoinduced heterogeneous processes.

A Systematic Knowledge of Nanoparticles and Nanotechnology - A Review

The main aim is to describe the journey to beautiful and useful word Nano. Nano stands for one billionth. In science & technology, Nano stands for one billionth of meter, 1nm-10-9 m. Nanoparticles and nanotechnology words are relatively new but nanoparticles themselves has been around and studied long before the word were used. The beautiful colours of stained glass windows are a result of the presence of small metal oxide clusters in glass, having a size comparable to the wavelength of light. Particles of different sizes scatter different wavelength of light, imparting different colours to the glass. In photography the small colloidal particles of silver are a part of the processes of image formation and water at ambient temperature consists of clusters of hydrogen bonded water molecules. The description of variation of properties of nanoparticle with size, practical application of nanotechnology, uses in defence and biotechnology and as well as disadvantage of nanotechnology are given in this article.

Crystal structures and properties of Fe(H2O)2[Ni(CN)4]·nH2O hydrates

We report the crystal structures and properties of iron hydrate compounds. These hydrates have 2D topologies and crystallize with three different structural features depending on the number of weakly bonded water molecules. Coordinated water molecules occupy the axial sites of the iron ion and support a network of hydrogen-bonded water molecules in the interlayer region. Crystal structures of these hydrates are known for Mn, Co, and Ni but not for Fe. The structure for the solids considered herein was solved and refined from powder XRD patterns complemented by IR, UV/Vis-NIR, Mössbauer, and TG data. The relevance of this structural study is related to the application of Hofmann-like coordination polymers as spin-crossover materials when the coordinated water molecules are replaced by dipyridines, pyridine, and derivatives that form pillars between adjacent layers. Upon dehydration of these solids, a reactive material is formed by assembly of tetrahedral iron ions with square planar nickel ions.

Specific versus Nonspecific Solvent Interactions of a Biomolecule in Water.

Solvent interactions, particularly hydration, are vital in chemical and biochemical systems. Model systems reveal microscopic details of such interactions. We uncover a specific hydrogen-bonding motif of the biomolecular building block indole (C8H7N), tryptophan's chromophore, in water: a strong localized N-H···OH2 hydrogen bond, alongside unstructured solvent interactions. This insight is revealed from a combined experimental and theoretical analysis of the electronic structure of indole in aqueous solution. We recorded the complete X-ray photoemission and Auger spectrum of aqueous-phase indole, quantitatively explaining all peaks through ab initio modeling. The efficient and accurate technique for modeling valence and core photoemission spectra involves the maximum-overlap method and the nonequilibrium polarizable-continuum model. A two-hole electron-population analysis quantitatively describes the Auger spectra. Core-electron binding energies for nitrogen and carbon highlight the specific interaction with a hydrogen-bonded water molecule at the N-H group and otherwise nonspecific solvent interactions.