Water Molecules In Liquid Phase Research Articles

Breakdown of the molecular orbital picture for X-ray emission of water

By measuring X-ray emission of the water molecule in liquid phase we establish a first example of K-shell X-ray emission spectra with strong breakdown of the molecular orbital picture. A complete splitting of the 2a1 peak into satellites is observed. A theoretical model with electronic configurations generated by coupled excitations/de-excitations, so-called semi-internal configuration interaction, captures the experimentally recorded features well. Differences with respect to the corresponding breakdown effect in ultraviolet photoelectron spectrum are highlighted. Molecular dynamics calculations indicate that solvent broadening can only make up for a small fraction of the width of the recorded 2a1 derived band.

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

Adsorption of Methylene Blue on Bituminous Coal: Adsorption Mechanism and Molecular Simulation

Coal with its complex porous medium and abundant oxygen functional groups could be used as an adsorbent to adsorb organic compounds. Adsorption experiments and molecular dynamics simulations were carried out to study the behavior of methylene blue (MB) on the surface of Wiser bituminous coal. The influence of adsorption through factors, such as pulverized coal dosage, adsorption reaction time, initial concentration, and temperature effect, was investigated. The removal efficiency of MB reached 96.5% under optimum reactive conditions. The adsorption equilibrium was accorded with a Langmuir isotherm adsorption equation. The adsorption of MB onto coal was a spontaneous process because the adsorption free energy ΔG0 was negative. It was consistent with the conclusion of a negative interaction energy between bituminous coal and MB obtained by molecular dynamics simulation. Moreover, the density distribution along z-axis of each component molecule showed that MB molecules were adsorbed on the coal surface because of the polar interactions between the methyl groups of MB and the hydrophilic sites at the coal surface. Also, the diffusion degree of water molecule in liquid phase showed that as MB molecules formed hydrogen bonds with the water molecules, the activity of water molecules was restricted.

Accuracy limit of rigid 3-point water models.

Classical 3-point rigid water models are most widely used due to their computational efficiency. Recently, we introduced a new approach to constructing classical rigid water models [S. Izadi et al., J. Phys. Chem. Lett. 5, 3863 (2014)], which permits a virtually exhaustive search for globally optimal model parameters in the sub-space that is most relevant to the electrostatic properties of the water molecule in liquid phase. Here we apply the approach to develop a 3-point Optimal Point Charge (OPC3) water model. OPC3 is significantly more accurate than the commonly used water models of same class (TIP3P and SPCE) in reproducing a comprehensive set of liquid bulk properties, over a wide range of temperatures. Beyond bulk properties, we show that OPC3 predicts the intrinsic charge hydration asymmetry (CHA) of water - a characteristic dependence of hydration free energy on the sign of the solute charge - in very close agreement with experiment. Two other recent 3-point rigid water models, TIP3PFB and H2ODC, each developed by its own, completely different optimization method, approach the global accuracy optimum represented by OPC3 in both the parameter space and accuracy of bulk properties. Thus, we argue that an accuracy limit of practical 3-point rigid non-polarizable models has effectively been reached; remaining accuracy issues are discussed.

Double differential cross sections for liquid water ionization by impact of fast electrons

SynopsisA theoretical study for the single ionization of water molecules in liquid phase by electron impact at high energies is presented. Through a first order model, we compute multiple differential cross sections considering an asymmetric coplanar geometry. The wavefunctions for a single liquid water molecule are obtained in a realistic way by using a Wannier orbital formalism. We compare our results with experiments for the vapor phase and previous theoretical results obtaining a good qualitative agreement.

Model potentials in liquid water ionization by fast electron impact

We study the ionization of water molecules in liquid phase by fast electron impact. We use our previous first-order model within an independent electron approximation that allows the reduction of the multielectronic problem into a monoelectronic one. The initial molecular states of the liquid water are represented in a realistic way through a Wannier orbital formalism. We complete our previous study by taking into account approximately the influence of the passive electrons of the target by means of different model potentials. We compute multiple differential cross sections for the most external orbital 1B1 and compare them with other results.

Triple differential cross sections for liquid water ionization by impact of fast electrons

A theoretical study for the ionization from several orbitals of the water molecules in liquid phase by electron impact is presented. Multiple differential cross sections are computed through a first order model considering an asymmetric coplanar geometry. The wavefunctions for a single liquid water molecule are obtained in a realistic way by using a Wannier orbital formalism. The comparison with previous theoretical results as well as experiments for the gas phase shows a qualitative agreement. Moreover, an analysis of the influence of the passive electrons is performed by the assistance of different static potentials.

Multiple differential cross sections for the ionization of liquid water molecules by fast electron impact

We present a theoretical study of single ionization of water molecules in liquid phase by impact of fast electron in a coplanar geometry. Multiple differential cross sections are computed through a first order model in a framework of an independent electron approximation. For the first time in this kind of study, the wavefunctions for a single water molecule in liquid phase are computed in a realistic way through a Wannier orbital formalism. A comparison with previous theoretical and experimental results, the latter corresponding to the gas phase, shows a good agreement. The main physical features of the reaction (such as binary and recoil peaks) are also observed in our results.

Ionization of liquid water by fast electron impact: multiple differential cross sections for the 1B1 orbital

We present a theoretical study of single ionization of water molecules in liquid phase by impact of fast electrons in a coplanar geometry. Multiple differential cross sections are obtained through a first order model obtained within the framework of an independent electron approximation in which relaxation of the target is not taken into account. The wavefunctions for a single water molecule in the liquid phase are obtained through a Wannier orbital formalism and the ejected electron is described by means of Coulomb functions. We also present averaged calculations over all molecular orientations. A comparison with previous theoretical and experimental results, the latter corresponding to water in gaz phase, shows a good agreement. The main physical features of the reaction (such as binary and recoil peaks) present in measurements for vapor are also observed in the present theoretical predictions.

Ultrafast dissociation of a core-ionized water molecule in liquid phase: Density functional theory based simulations

We investigate the dynamics of a core-ionized molecule in liquid water by performing first-principles density functional theory (DFT)-based simulations. We observe that molecular dissociation is reached within the lifetime of the induced vacancy. Our findings show that at least one of the intramolecular hydrogens migrates from the core- ionized molecule to one molecule of the first solvation shell.

Differential cross sections for single ionization of water molecules in liquid phase by electron impact at high impact energies

We compute Differential Cross Sections (DCS) for single ionization of fixed-in-space liquid water by electron impact at high impact energies. Several orientations of the molecule are considered. The DCS for different molecular orbitals exhibit a strong dependence with the molecular orientation.

Two Algorithms for Defining Atoms and Molecules in Condensed Phases

Two algorithms for defining single entities in condensed phase based on the calculation of a zero flux surface of the gradient of the electron density are proposed. First the two approaches are applied to a water molecule in a liquid system; the different behaviour of the two algorithms is graphically shown in the planar section of the molecular plane (i.c., HOH plane of the molecule analyzed). Next, using the two algorithms for partitioning electron density, the average molecular dipole moment of the water molecule in liquid phase is calculated averaging over several configurations; analogies and differences with other methods are reported and their physical interpretation is discussed. There exist different approaches for calculating the zero flux surface (or equivalently the volume defined by such a surface); the two described in this work differ from the others because the calculation in both cases is straightforward (i.e., the surface is determined directly from the data corresponding to the electron density) and is characterized by a relatively short computational time.

Mixed quantum—classical calculations on the water molecule in liquid phase: Influence of a polarizable environment on electronic properties

Mixed quantum—classical calculations on the water molecule in liquid phase: Influence of a polarizable environment on electronic properties

Mixed quantum?classical calculations on the water molecule in liquid phase: Influence of a polarizable environment on electronic properties

Mixed quantum?classical calculations on the water molecule in liquid phase: Influence of a polarizable environment on electronic properties