Protons In Liquid Water Research Articles

ZundEig: The Structure of the Proton in Liquid Water from Unsupervised Learning.

The structure of the excess proton in liquid water has been the subject of lively debate on both experimental and theoretical fronts for the last century. Fluctuations of the proton are typically interpreted in terms of limiting states referred to as the Eigen and Zundel species. Here, we put these ideas under the microscope, taking advantage of recent advances in unsupervised learning that use local atomic descriptors to characterize environments of acidic water combined with advanced clustering techniques. Our agnostic approach leads to the observation of only one charged cluster and two neutral ones. We demonstrate that the charged cluster involving the excess proton is best seen as an ionic topological defect in water's hydrogen bond network, forming a single local minimum on the global free-energy landscape. This charged defect is a highly fluxional moiety, where the idealized Eigen and Zundel species are neither limiting configurations nor distinct thermodynamic states. Instead, the ionic defect enhances the presence of neutral water defects through strong interactions with the network. We dub the combination of the charged and neutral defect clusters as ZundEig, demonstrating that the fluctuations between these local environments provide a general framework for rationalizing more descriptive notions of the proton in the existing literature.

Real-Time Electron Solvation Induced by Bursts of Laser-Accelerated Protons in Liquid Water.

Understanding the mechanisms of proton energy deposition in matter and subsequent damage formation is fundamental to radiation science. Here we exploit the picosecond (10^{-12} s) resolution of laser-driven accelerators to track ultrafast solvation dynamics for electrons due to proton radiolysis in liquid water (H_{2}O). Comparing these results with modeling that assumes initial conditions similar to those found in photolysis reveals that solvation time due to protons is extended by >20 ps. Supported by magnetohydrodynamic theory this indicates a highly dynamic phase in the immediate aftermath of the proton interaction that is not accounted for in current models.

Microdosimetry and Dose-Averaged LET Calculations of Protons in Liquid Water: A Novel Geant4-DNA Application

The spatial distribution of energy deposition events is an essential aspect in the determination of the radiobiological effects of ionizing radiation at the cellular level. Microdosimetry provides a theoretical framework for the description of these events, and has been used in several studies to address problems such as the characterization of Linear Energy Transfer (LET) and Relative Biological Effectiveness (RBE) of ion beams for proton therapy applications. Microdosimetry quantities and their distributions can be obtained by means of Monte Carlo simulations. In this work, we present a track structure Monte Carlo (MC) application, based on Geant4-DNA, for the computation of microdosimetric distributions of protons in liquid water. This application provides two sampling methods uniform and weighted, for the scoring of the quantities of interest in spherical sites, with diameters ranging from 1 to 10 μm. As an element of novelty, the work shows the approach followed to calculate, without resorting to dedicated simulations, the distribution of energy imparted to the site per electronic collision of the proton, which can be used to obtain the macroscopic dose-averaged LET as proposed by Kellerer. Furthermore, in this work the concept of effective mean chord length is proposed to take into account δ-ray influx and escape in the calculation of macroscopic dose-averaged LET for proton track segments and retrieve the agreement predicted by Kellerer’s formula. Finally, the results obtained demonstrate that our MC application is reliable and computational-efficient to perform calculations of microdosimetric distributions and dose-averaged LET of proton track segments in liquid water.

Efficient ab initio calculation of electronic stopping in disordered systems via geometry pre-sampling: Application to liquid water

Knowledge of the electronic stopping curve for swift ions, Se(v), particularly around the Bragg peak, is important for understanding radiation damage. Experimentally, however, the determination of such a feature for light ions is very challenging, especially in disordered systems such as liquid water and biological tissue. Recent developments in real-time time-dependent density functional theory (rt-TDDFT) have enabled the calculation of Se(v) along nm-sized trajectories. However, it is still a challenge to obtain a meaningful statistically averaged Se(v) that can be compared to observations. In this work, taking advantage of the correlation between the local electronic structure probed by the projectile and the distance from the projectile to the atoms in the target, we devise a trajectory pre-sampling scheme to select, geometrically, a small set of short trajectories to accelerate the convergence of the averaged Se(v) computed via rt-TDDFT. For protons in liquid water, we first calculate the reference probability distribution function (PDF) for the distance from the proton to the closest oxygen atom, ϕR(rp→O), for a trajectory of a length similar to those sampled experimentally. Then, short trajectories are sequentially selected so that the accumulated PDF reproduces ϕR(rp→O) to increasingly high accuracy. Using these pre-sampled trajectories, we demonstrate that the averaged Se(vp) converges in the whole velocity range with less than eight trajectories, while other averaging methods using randomly and uniformly distributed trajectories require approximately ten times the computational effort. This allows us to compare the Se(vp) curve to experimental data and assess widely used empirical tables based on Bragg’s rule.

Proton NMR relaxation from molecular dynamics: intramolecular and intermolecular contributions in water and acetonitrile.

NMR relaxation rates for protons in liquid water and neat acetonitrile were computed based on ab initio molecular dynamics (aiMD) with forces from Kohn-Sham (KS) theory as well as force-field (FF) based classical dynamics. Intra- and intermolecular dipole-dipole contributions were separated, and nearly quantitative agreement with experiment was obtained for water. Spin-rotation (SR) contributions to the intramolecular relaxation rate in acetonitrile were computed using nuclear SR coupling tensors obtained from KS theory. Their inclusion improved the total computed intramolecular rate to within a factor of two of experiment. Insufficient sampling of rare short-time collision events between neighboring acetonitrile molecules in the simulations is hypothesized as a major source of error in the intermolecular contributions.

A method for range calculation of proton in liquid water: Validation study using Monte Carlo method and NIST data

Introduction: The main advantage of using ion beams over photons in radiotherapy is due to their inverse depth-dose profiles, allowing higher doses to tumors, while better sparing normal tissues. When calculating dose distributions with ion beams, one crucial point is the uncertainty of the Bragg-peak range. Recently great effort is devoted to enhance the accuracy of the computation for proton treatments without increasing the calculation time. The highest accuracy in these calculations is obtained by Monte Carlo simulation methods. GATE is a Monte Carlo simulation platform based on geant4 which was found to be a convenient simulation environment to perform this study. This study shows how a stochastic method such as Monte Carlo can be utilized to obtain certain quantities of practical importance related to charged particle transport Materials and Methods: In this study, GATE code was used to compute absorbed dose and fluence of protons in the energy range of 50-200 MeV and with energy step of 50 MeV. A water phantom (40*40*40 cm3) was modeled in a vacuum world volume (5*5*5 m3). Several physics lists have been defined in the GATE code that we used FTFP_BERT. The mono-energetic protons were emitted mono-directionally from a point source at one end of the water phantom. The simulations were carried out for 10^6 proton histories that yielded better than 0.3% statistical errors. Results: In this study, we validated the Gate code in proton therapy applications. This study examined different physics lists and showed that the results obtained using FTFP_BERT physics are in a good agreement with NIST database. Our Results were compared to the CSDA ranges from NIST database using the GATE simulation code. The FTFP_BERT results showed good agreement within 1% for energies higher than 30 MeV and within 0.1% for energies higher than 70 MeV .We also conclude that the value of 0.1 mm is optimal for the SetCut. Conclusion: The results were found to be ±0.1% compared to the data from the NIST compilation. It is safe to conclude that this approach can be extended to determine dosimetric quantities for other media, energies and charged particle types.

Decomposition of the Experimental Raman and Infrared Spectra of Acidic Water into Proton, Special Pair, and Counterion Contributions.

Textbooks describe excess protons in liquid water as hydronium (H3O+) ions, although their true structure remains lively debated. To address this question, we have combined Raman and infrared (IR) multivariate curve resolution spectroscopy with ab initio molecular dynamics and anharmonic vibrational spectroscopic calculations. Our results are used to resolve, for the first time, the vibrational spectra of hydrated protons and counterions and reveal that there is little ion-pairing below 2 M. Moreover, we find that isolated excess protons are strongly IR active and nearly Raman inactive (with vibrational frequencies of ∼1500 ± 500 cm-1), while flanking water OH vibrations are both IR and Raman active (with higher frequencies of ∼2500 ± 500 cm-1). The emerging picture is consistent with Georg Zundel's seminal work, as well as recent ultrafast dynamics studies, leading to the conclusion that protons in liquid water are primarily hydrated by two flanking water molecules, with a broad range of proton hydrogen bond lengths and asymmetries.

IR spectral assignments for the hydrated excess proton in liquid water

The local environmental sensitivity of infrared (IR) spectroscopy to a hydrogen-bonding structure makes it a powerful tool for investigating the structure and dynamics of excess protons in water. Although of significant interest, the line broadening that results from the ultrafast evolution of different solvated proton-water structures makes the assignment of liquid-phase IR spectra a challenging task. In this work, we apply a normal mode analysis using density functional theory of thousands of proton-water clusters taken from reactive molecular dynamics trajectories of the latest generation multistate empirical valence bond proton model (MS-EVB 3.2). These calculations are used to obtain a vibrational density of states and IR spectral density, which are decomposed on the basis of solvated proton structure and the frequency dependent mode character. Decompositions are presented on the basis of the proton sharing parameter δ, often used to distinguish Eigen and Zundel species, the stretch and bend character of the modes, the mode delocalization, and the vibrational mode symmetry. We find there is a wide distribution of vibrational frequencies spanning 1200-3000 cm-1 for every local proton configuration, with the region 2000-2600 cm-1 being mostly governed by the distorted Eigen-like configuration. We find a continuous red shift of the special-pair O⋯H+⋯O stretching frequency, and an increase in the flanking water bending intensity with decreasing δ. Also, we find that the flanking water stretch mode of the Zundel-like species is strongly mixed with the flanking water bend, and the special pair proton oscillation band is strongly coupled with the bend modes of the central H5O2+moiety.

, M. L. Bouhssa and Z. Houssni

, M. L. Bouhssa and Z. Houssni

Electronic Excitation Dynamics in Liquid Water under Proton Irradiation

Molecular behaviour of liquid water under proton irradiation is of great importance to a number of technological and medical applications. The highly energetic proton generates a time-varying field that is highly localized and heterogeneous at the molecular scale, and massive electronic excitations are produced as a result of the field-matter interaction. Using first-principles quantum dynamics simulations, we reveal details of how electrons are dynamically excited through non-equilibrium energy transfer from highly energetic protons in liquid water on the atto/femto-second time scale. Water molecules along the path of the energetic proton undergo ionization at individual molecular level, and the excitation primarily derives from lone pair electrons on the oxygen atom of water molecules. A reduced charge state on the energetic proton in the condensed phase of water results in the strongly suppressed electronic response when compared to water molecules in the gas phase. These molecular-level findings provide important insights into understanding the water radiolysis process under proton irradiation.

The Hydrated Excess Proton in the Zundel Cation H5O2+: The Role of Ultrafast Solvent Fluctuations

AbstractThe nature of the excess proton in liquid water has remained elusive after decades of extensive research. In view of ultrafast structural fluctuations of bulk water scrambling the structural motifs of excess protons in water, we selectively probe prototypical protonated water solvates in acetonitrile on the femtosecond time scale. Focusing on the Zundel cation H5O2+ prepared in room‐temperature acetonitrile, we unravel the distinct character of its vibrational absorption continuum and separate it from OH stretching and bending excitations in transient pump‐probe spectra. The infrared absorption continuum originates from a strong ultrafast frequency modulation of the H+ transfer vibration and its combination and overtones. Vibrational lifetimes of H5O2+ are found to be in the sub‐100 fs range, much shorter than those of unprotonated water. Theoretical results support a picture of proton hydration where fluctuating electrical interactions with the solvent and stochastic thermal excitations of low‐frequency modes continuously modify the proton binding site while affecting its motions.

The Hydrated Excess Proton in the Zundel Cation H5 O2 (+) : The Role of Ultrafast Solvent Fluctuations.

The nature of the excess proton in liquid water has remained elusive after decades of extensive research. In view of ultrafast structural fluctuations of bulk water scrambling the structural motifs of excess protons in water, we selectively probe prototypical protonated water solvates in acetonitrile on the femtosecond time scale. Focusing on the Zundel cation H5 O2 (+) prepared in room-temperature acetonitrile, we unravel the distinct character of its vibrational absorption continuum and separate it from OH stretching and bending excitations in transient pump-probe spectra. The infrared absorption continuum originates from a strong ultrafast frequency modulation of the H(+) transfer vibration and its combination and overtones. Vibrational lifetimes of H5 O2 (+) are found to be in the sub-100 fs range, much shorter than those of unprotonated water. Theoretical results support a picture of proton hydration where fluctuating electrical interactions with the solvent and stochastic thermal excitations of low-frequency modes continuously modify the proton binding site while affecting its motions.

A Quasi-Elastic Neutron Scattering Study of the Dynamics of Electrically Constrained Water.

We have measured the quasi-elastic neutron scattering (QENS) of an electrohydrodynamic liquid bridge formed between two beakers of pure water when a high voltage is applied, a setup allowing to investigate water under high-voltage without high currents. From this experiment two proton populations were distinguished: one consisting of protons strongly bound to oxygen atoms (immobile population, elastic component) and a second one of quasi-free protons (mobile population, inelastic component) both detected by QENS. The diffusion coefficient of the quasi-free protons was found to be D = (26 ± 10) × 10(-5) cm(2) s(-1) with a jump length lav ∼ 3 Å and an average residence time of τ0 = 0.55 ± 0.08 ps. The associated proton mobility in the proton channel of the bridge is ∼9.34 × 10(-7) m(2) V(-1) s(-1), twice as fast as diffusion-based proton mobility in bulk water. It also matches the so-called electrohydrodynamic or "apparent" charge mobility, an experimental quantity which so far has lacked molecular interpretation. These results further corroborate the proton channel model for liquid water under high voltage and give new insights into the molecular mechanisms behind electrohydrodynamic charge transport phenomena and delocalization of protons in liquid water.

Ultrafast 2D IR spectroscopy of the excess proton in liquid water.

Despite decades of study, the structures adopted to accommodate an excess proton in water and the mechanism by which they interconvert remain elusive. We used ultrafast two-dimensional infrared (2D IR) spectroscopy to investigate protons in aqueous hydrochloric acid solutions. By exciting O-H stretching vibrations and detecting the spectral response throughout the mid-IR region, we observed the interaction between the stretching and bending vibrations characteristic of the flanking waters of the Zundel complex, [H(H2O)2](+), at 3200 and 1760 cm(-1), respectively. From time-dependent shifts of the stretch-bend cross peak, we determined a lower limit on the lifetime of this complex of 480 femtoseconds. These results suggest a key role for the Zundel complex in aqueous proton transfer.

Lateral spread of dose distribution by therapeutic proton beams in liquid water

We have calculated the lateral spread of the dose distribution of protons in liquid water by means of the SEICS (Simulation of Energetic Ions and Clusters through Solids) code, which properly accounts for the electronic stopping force (including energy-loss straggling), multiple elastic scattering with the target nuclei, dynamical electron charge-exchange processes and nuclear fragmentation reactions between the projectile and the nuclei of the target. Due to the multiple elastic scattering processes part of the proton energy may be deposited at a given lateral distance from the initial beam direction, which is quantified by the root mean square radius (rrms). We find in our simulations that the rrms follows a parabolic dependence as a function of the depth in the target and the quotient between the rrms at the Bragg peak and the depth of the Bragg peak is around 3% independently of the proton energy. A rather good agreement is obtained when comparing our results of rrms with experimental data and with other models.

The calculation of proton and secondary electron stopping powers in liquid water

The stopping power of energetic protons in liquid water has been calculated using a new model based on different theoretical and semi-empirical approaches. In this model, we consider the relativistic corrections along with the electronic and nuclear stopping power.The present work accounts for the different interactions made with electrons and nuclei inside the target. Interactions of the incident particle with the target's electrons dominate in the high energy regime; in the low energy regime, the interactions of the projectile with the target nuclei contribute importantly and are included in the calculation.We also compute the stopping cross sections and the stopping power of secondary electrons ejected from proton and hydrogen ionization impact, and generated by hydrogen electron loss processes. The consideration of secondary electrons' stopping power can contribute to the study of nano-dosimetry.Our results are in good agreement with existing experimental data. This calculation model can be useful for different applications in medical physics and space radiation health, such as hadron therapy for cancer treatment or radiation protection for astronauts.

Energy loss measurement of protons in liquid water

The proton stopping power of liquid water was, for the first time, measured in the energy range 4.7–15.2 MeV. The proton energies were determined by the time-of-flight transmission technique with the microchannel plate detectors, which were especially developed for timing applications. The results are compared to the literature values (from ICRU Report 49 (1993) and Janni's tabulation (1982 At. Data Nucl. Data Tables 27 147–339)) which are based on Bethe's formula and an agreement is found within the experimental uncertainty of 4.6%. Thus, earlier reported discrepancy between the experimental and literature stopping power values at lower energies was not observed at the energies considered in this experiment.

Off-resonance effects in surface nuclear magnetic resonance

Surface nuclear magnetic resonance (NMR) is a noninvasive geophysical tool used to investigate groundwater reservoirs. The relevant physical process in surface NMR is the nuclear spin of hydrogen protons in liquid water. Standard single-pulse surface NMR experiments provide estimates of water content in the shallow subsurface. Under favorable conditions, pore-structure and even hydraulic-conductivity information can be extracted from double-pulse surface NMR data. One crucial issue in surface NMR experiments is the resonance condition: the frequency of the excitation field should closely match the Larmor frequency of the protons, which is controlled by the local magnitude of the earth’s magnetic field. Although the earth’s field can be measured accurately by an on-site magnetometer, several effects impede perfect matching of the frequencies. These include temporal variations of the earth’s field, instrumental imperfections, and the magnetic susceptibility of the underlying rocks. We assess the impact of violating the resonance condition on surface NMR experiments. Our investigation involves numerical simulations and measurements using a sample-scale earth-field NMR device and a surface NMR acquisition system. For frequency offsets up to 5 Hz, we find that relatively standard single-pulse surface NMR recording procedures are likely to produce reliable water-content estimates as long as the pulse moments are small to moderate or the aquifer is relatively deep. If strong pulse moments are required or shallow aquifers are probed, off-resonance conditions can lead to anomalous increases in recorded amplitudes that can be mistakenly interpreted in terms of deepwater occurrences. Double-pulse surface NMR experiments are particularly sensitive to off-resonance effects, such that the results may be highly biased even for the small-frequency offsets commonly encountered in field situations.

Infrared Spectrum of the Hydrated Proton in Water.

Reactive molecular dynamics simulations have been utilized to calculate the infrared (IR) spectra of acidic HCl solutions of varying concentration with the goal of achieving a better understanding of the spectral features of the hydrated excess protons in bulk water. To incorporate the essential physics of the hydrated proton, we carried out the simulations using the specialized self-consistent iterative multistate empirical valence bond (SCI-MS-EVB) method, which is a form of multiconfigurational (reactive) molecular dynamics. After the pure water absorption background was removed, the calculated difference spectra are in good agreement with prior experimental results. The continuous broad absorption band in the acidic IR spectrum is, for the first time, interpreted based on the concept of a dynamically distorted Eigen cation, H9O4(+), which has been shown to provide the most accurate description for the charge defect character of the hydrated excess proton in liquid water.

Stopping cross sections of liquid water for MeV energy protons

Cross sections for the stopping of swift protons in liquid water have been measured for the first time by using a liquid water jet target of 50 μm in diameter. The energy loss spectra of incident 2.0 MeV protons were measured at scattering angles of 5.0–50 mrad. Experimental energy loss spectra have been successfully reproduced by Monte Carlo simulation calculations (GEANT4.9.1.p02 toolkit) by taking account of multiple scattering of projectile ions inside the liquid water target. The present stopping cross sections are found to be considerably smaller than other standard stopping power data, revealing e.g. about 11% deviation from those of SRIM2003.