Electrons In Liquid Water Research Articles

Collision of Incident Electrons with Liquid Water Molecules: Study of Linear Energy Transfer (LET)

We used GAMOS software to simulate the interaction of electrons in liquid water. In our work, the chosen parameter, the Linear Energy Transfer (LET), is studied in an energy range from 2.5 eV to 100 MeV. The results obtained were analyzed and compared with experimental data and literature. A very good agreement emerged.
 Also the analysis of the LET curve of the medium crossed presents a maximum of 37.0626 MeV/mm corresponding to an electron energy of 102.447 eV. For energies below this value, the energy loss is greater. On the other hand, for energies higher than this value, there is less energy loss.

Reduction of CO2 with Hydrated Electrons: Ab Initio Computational Studies for Finite-Size Cluster Models.

In the present work, the mechanisms of the reduction of the CO2 molecule with hydrated electrons to the hydroxyl-formyl (HOCO) radical were studied with ab initio computational methods. Hydrated hydronium radicals, H3O(H2O)n (n = 0,3,6), are considered as finite-size models of the hydrated electron in liquid water. The investigation of cluster models allows the application of high-accuracy electronic-structure methods, which are not computationally feasible in condensed-phase simulations. Reaction paths and potential-energy (PE) profiles of the proton-coupled electron-transfer reaction from hydrated H3O radicals to the CO2 molecule were explored on the ground-state PE surface. The computationally efficient unrestricted second-order Møller-Plesset method is employed, and its accuracy has been carefully benchmarked in comparison with complete-active-space self-consistent-field and multi-reference second-order perturbation calculations. The results provide insights into the interplay of electron transfer from the diffuse Rydberg-type unpaired electron of H3O to the CO2 molecule, the contraction of the electron cloud by the re-hybridization of the carbon atom of CO2, and proton transfer from the nearest water molecule to the CO2- anion, followed by Grotthus-type proton rearrangements to form stable clusters. Starting from local energy minima of hydrogen-bonded CO2-H3O(H2O)n complexes, the reaction to form HOCO-(H2O)n+1 complexes is exothermic by about 1.3 eV (125 kJ/mol). The reaction is barrier controlled with a barrier of the order of a few tenths of an electron volt, depending on size and conformation of the water cluster. This barrier is at least an order of magnitude lower than the barrier of the reaction of CO2 with any closed-shell partner molecule. The HOCO radicals can recombine by H-atom transfer (disproportionation), resulting in formic acid or a dihydroxycarbene product, as well as by the formation of a C-C bond, resulting in oxalic acid. The strong exothermicity of these radical-radical recombination reactions likely results in the fragmentation of the closed-shell products formic acid and oxalic acid, which explains the strong specificity for CO formation observed in recent experiments of Hamers and co-workers.

Distortion Correction of Low-Energy Photoelectron Spectra of Liquids Using Spectroscopic Data for Solvated Electrons.

Time-resolved photoelectron spectroscopy (TRPES) enables real-time observation of ultrafast electronic dynamics in solutions. When extreme ultraviolet (EUV) probe pulses are employed, they can ionize solutes from all electronic states involved in the dynamics. However, EUV pulses also produce a strong ionization signal from a solvent that is typically 6 orders of magnitude greater than the pump-probe photoelectron signal of solutes. Alternatively, UV probe pulses enable highly sensitive and selective observation of photoexcited solutes because typical solvents such as water are transparent to UV radiation. An obstacle in such UV-TRPES measurements is spectral distortion caused by electron scattering and a yet to be identified mechanism in liquids. We have previously proposed the spectral retrieval (SR) method as an a posteriori approach to removing the distortion and overcoming this difficulty in UV-TRPES; however, its accuracy has not yet been verified by comparison with EUV-TRPES results. In the present study, we perform EUV-TRPES for charge transfer reactions in water, methanol, and ethanol, and verify SR analysis of UV-TRPES. We also estimate a previously undetermined energy-dependent intensity factor and expand the basis sets for SR analysis. The refined SR method is employed for reanalyzing the UV-TRPES data for the formation and relaxation dynamics of solvated electrons in various systems. The electron binding energy distributions for solvated electrons in liquid water, methanol, and ethanol are confirmed to be Gaussian centered at 3.78, 3.39, and 3.25 eV, respectively, in agreement with Nishitani et al. [ Sci. Adv. 2019, 5(8), eaaw6896]. An effective energy gap between the conduction band and the vacuum level at the gas-liquid interface is estimated to be 0.2 eV for liquid water and 0.1 eV for methanol and ethanol.

Sub-keV corrections to binary encounter cross section models for electron ionization of liquid water with application to the Geant4-DNA Monte Carlo code

IntroductionThe electron ionization cross section of water is one of the most important input in Monte Carlo studies of cellular radiobiological effects. Analytical cross section models of the binary-encounter type have the potential of reducing simulation time and facilitate application to a variety of biological materials (other than water). The Binary-Encounter-Bethe (BEB) and Binary-Encounter-Dipole (BED) models of NIST are perhaps the most popular of such models giving reliable results for atoms and molecules in the gas-phase over a wide energy range. However, the use of such models to sub-keV electron energies in liquid water raises concerns due to the neglect of condensed phase effects that leads to a significant overestimation when compared to medium-specific dielectric models. PurposeTo modify the BEB and BED models towards better agreement with the recommended low-energy dielectric model of Geant4-DNA (Option 4). To implement the new modifications to the existing BEB model of the Option 6 physics constructor of Geant4-DNA and re-evaluate fundamental transport quantities for sub-keV electrons. MethodsIn analogy to a Yukawa potential a simple, yet physically-motivated, modification of the Burgess correction term is proposed to account for the reduction of the Coulomb interaction due to the polarizability of the target. The magnitude of the correction is guided by the dielectric-based ionization cross section implemented in Option 4. ResultsDifferential, total and stopping ionization cross sections for low-energy electrons in liquid water are presented. When combined with the Vriens correction (which is not included in Option 6), the proposed modification to the BEB and BED models brings the ionization and stopping cross sections in much better agreement against those used in the Option 4 dielectric model of Geant4-DNA, with up to 30% and 10% deviation, respectively. Implementation of the new correction to the Option 6 constructor of Geant4-DNA and re-evaluation of fundamental transport quantities, such as electron penetration ranges and dose-point-kernels, reduced the discrepancies from Option 4 at sub-keV energies from 20 to 100% (or more) to well below 10% in most cases. ConclusionsA simple modification to the BEB and BED analytic models was found to improve their performance for sub-keV electrons in liquid water medium. Implementation of the new modification to the Option 6 constructor of Geant4-DNA significantly improved the agreement with the recommended low-energy Option 4 constructor for a variety of fundamental quantities related to electron transport.

Research on the proximity functions of microdosimetry of low energy electrons in liquid water based on different Monte Carlo codes

PurposeThe proximity function is an important index in microdosimetry for describing the spatial distribution of energy, which is closely related to the biological effects of organs or tissues in the target area. In this work, the impact of parameters, such as physic models, cut-off energy, and initial energy, on the proximity function are quantitated and compared. MethodsAccording to the track structure (TS) and condensed history (CH) low-energy electromagnetic models, this paper chooses a variety of Monte Carlo (Monte Carlo, MC) codes (Geant4-DNA, PHITS, and Penelope) to simulate the track structure of low-energy electrons in liquid water and evaluates the influence of the electron initial energy, cut-off energy, energy spectrum, and physical model factors on the differential proximity function. ResultsThe results show that the initial energy of electrons in the low-energy part (especially less than 1 keV) has a greater impact on the differential proximity function, and the choice of cut-off energy has a greater impact on the differential proximity function corresponding to small radius sites (generally less than 10 nm). The difference in the electronic energy spectrum has little effect on the result, and the proximity functions of different physics models show better consistency under large radius sites. ConclusionsThis work comprehensively compares the differential proximity functions under different codes by setting a variety of simulation conditions and has basic guiding significance for helping users simulate and analyze the deposition characteristics of microscale electrons according to the selection of an appropriate methodology and cut-off energy.

Accurate Vertical Ionization Energy of Water and Retrieval of True Ultraviolet Photoelectron Spectra of Aqueous Solutions.

Ultraviolet (UV) photoelectron spectroscopy provides a direct way of measuring valence electronic structure; however, its application to aqueous solutions has been hampered by a lack of quantitative understanding of how inelastic scattering of low-energy (<5 eV) electrons in liquid water distorts the measured electron kinetic energy distributions. Here, we present an efficient and widely applicable method for retrieving true UV photoelectron spectra of aqueous solutions. Our method combines Monte Carlo simulations of electron scattering and spectral inversion, with molecular dynamics simulations of depth profiles of organic solutes in aqueous solution. Its application is demonstrated for both liquid water, and aqueous solutions of phenol and phenolate, which are ubiquitous biologically relevant structural motifs.

Status and Extension of the Geant4-DNA Dielectric Models for Application to Electron Transport

The development of accurate physics models that enable track structure simulations of electrons in liquid water medium over a wide energy range, from the eV to the MeV scale, is a subject of continuous efforts due to its importance (among other things) in theoretical studies of radiation quality for application in radiotherapy and radiation protection. A few years ago, the Geant4-DNA very low-energy extension of the Geant4 Monte Carlo code had offered to users an improved set of physics models for discrete electron transport below 10 keV. In this work we present refinements to this model set and its extension to energies up to 1 MeV. Preliminary comparisons against the existing Geant4-DNA physics models with respect to total and differential ionization cross sections of electrons in liquid water are reported and discussed.

Stopping power and CSDA range of electrons in liquid water, LiF, CaF2, and Al2O3 from the energy gap up to 433 keV

Stopping powers (SP) for electrons with energies greater than 10 keV are well described through the Bethe approximation. However, for energies below, such an approach is inadequate. SP in LiF, CaF2 and Al2O3 as the luminescent materials commonly used for dosimetry study and liquid-water are scarce at energies below 10 keV. This work investigated SP and CSDA-range of electrons in in these compounds from the energy gap up to 433 keV using the full Penn algorithm. In particular, the influence of the exciton states was evaluated. The experimental optical data were selected after a rigorous evaluation process. The results indicate that the exciton states affect the SP mainly at energies below 100 eV by up to 48%, 39%, 32% and 15% for liquid-water, LiF, CaF2 and Al2O3, respectively. Furthermore, we observed a certain relationship between the minimum excitation-energy (exciton state) and the energy at which the SP is maximum.

Monte Carlo simulation of electrons injected from a low-temperature plasma into liquid water

When electrons from a plasma enter a water surface, they collide with the water molecules and lose their energy, eventually becoming hydrated electrons, which are an important species for radical formation in liquid water. Although gas discharge plasmas in contact with water are an easy source of hydrated electrons, their production processes are not clearly understood. In this study, Monte Carlo simulations of electrons in liquid water were performed to investigate the production of a hydrated electron and radical species by low-energy electron irradiation of the water surface from an atmospheric-pressure plasma. The incident electrons were assumed to have a Maxwellian energy distribution with mean electron energy ranging from 1 to 10 eV. The production of hydrated electrons by electron irradiation of 3 eV reached a peak near the gas–liquid interface, and the electrons spread to a depth of approximately 17 nm. OH and H are also generated near the water surface.

Terahertz Polaron Oscillations of Electrons Solvated in Liquid Water.

The terahertz (THz) response of solvated electrons in liquid water is studied in nonlinear ultrafast pump-probe experiments. Free electrons with concentrations from c_{e}=4 to 140×10^{-6} moles/liter are generated by high-field THz or near-infrared multiphoton excitation. The time-resolved change of the dielectric function as mapped by broadband THz pulses exhibits pronounced oscillations persisting up to 30ps. Their frequency increases with electron concentration from 0.2 to 1.5THz. The oscillatory response is assigned to impulsively excited coherent polarons involving coupled electron and water shell motions with a frequency set by the local electric field.

Can Current Experimental Data Exclude Non-Gaussian Genuine Band Shapes in Ultraviolet Photoelectron Spectra of the Hydrated Electron?

Two recent articles present results that allegedly exclude a possible multimodal distribution of the hydrated electron in ultraviolet photoelectron spectra. The first article bases its conclusion on the assumption that the non-Gaussian genuine band shape previously retrieved for the solvated electron in liquid water is an artifact arising from insufficient electron scattering cross sections used in the retrieval. The second article excludes a multimodal band shape based on a photoelectron spectrum of the solvated electron in water clusters recorded at a single ultraviolet photon energy, and it further assumes that cluster results are transferable to the liquid without further justification. Here, we show that based on current data multimodal distributions cannot be unambiguously excluded. Furthermore, the transferability of cluster results to the liquid can be neither justified nor refuted on the basis of currently available experimental ultraviolet photoelectron spectra.

Alternative Approach for the Determination of Mean Free Paths of Electron Scattering in Liquid Water Based on Experimental Data.

Mean free paths of low-energy electrons in liquid water are of importance for modeling many physicochemical processes, but neither theoretical predictions nor experimental results have converged for these parameters. We therefore introduce an approach to determine elastic and inelastic mean free paths (EMFP, IMFP) based on experimental data. We show that ab initio calculations of electron scattering with water clusters converge with cluster size, thus providing access to condensed-phase scattering. The results are used in Monte Carlo simulations to extract EMFP and IMFP from recent liquid-microjet experiments that determined the effective attenuation length (EAL) and the photoelectron angular distribution (PAD) following oxygen 1s-ionization of liquid water. For electron kinetic energies from 10 to 300 eV, we find that the IMFP is noticeably larger than the EAL. The EMFP is longer than that of gas-phase water and the IMFP is longer compared to latest theoretical estimations, but both EMFP and IMFP are much shorter than suggested by experimental measurements of integral cross sections for amorphous ice.

A comparative study on Monte Carlo simulations of electron emission from liquid water.

Liquid water being the major constituent of the human body, is of fundamental importance in radiobiological research. Hence, the knowledge of electron-water interaction physics and particularly the secondary electron yield is essential. However, to date, only very little is known experimentally on the low energy electron interaction with liquid water because of certain practical limitations. The purpose of this study was to gain some useful information about electron emission from water using a Monte Carlo (MC) simulation technique that can numerically model electron transport trajectories in water. In this study, we have performed MC simulations of electron emission from liquid water in the primary energy range of 50eV-30keV by using two different codes, i.e., a classical trajectory MC (CMC) code developed in our laboratory and the Geant4-DNA (G4DNA) code. The calculated secondary electron yield and electron backscattering coefficient are compared with experimental results wherever applicable to verify the validity of physical models for the electron-water interaction. The secondary electron yield vs. primary energy curves calculated using the two codes present the same generic curve shape as that of metals but in rather different absolute values. G4DNA underestimates the secondary electron yield due to the application of one step thermalization model by setting a cutoff energy at 10eV so that the low energy losses due to phonon excitations are omitted. Our CMC code, using a full energy loss spectrum to model electron inelastic scattering, allows the simulation of individual phonon scattering events for very low energy losses down to 10 meV, which then enables the calculated secondary electron yields much closer to the experimental data and also gives quite reasonable energy distribution curve of secondary electrons. It is concluded that full dielectric function data at low energy loss values below 10eV are recommended for modeling of low energy electrons in liquid water.

The influence of Geant4-DNA toolkit parameters on electron microdosimetric track structure.

The influence of different physical process factors on tracks of low-energy electrons in liquid water was analyzed and evaluated based on the Geant4-DNA toolkit of Geant4 version 10.4, and it provides theoretical support for obtaining the basic parameters of microdosimetry concerned with radiotherapy and radiation protection. According to the characteristics of different models, five physics constructors of Geant4-DNA toolkit were selected to simulate monoenergetic electrons in microscopic scale. Details of track structure of different Geant4-DNA physics constructors were compared, including total number of interaction processes, number and energy percentage of excitation and ionization; analyzing the impacts of mean lineal energy of several factors, including Geant4-DNA physics constructors, initial energy, radius of scoring spheres, interaction processes and cut-off energy. Firstly, ‘G4EmDNAPhysics’ (hereinafter referred to as ‘dna’) is well consistent with ‘G4EmDNAPhysics_option 2’ (hereinafter referred to as ‘option 2’), and ‘G4EmDNAPhysics_option 4’ (hereinafter referred to as ‘option 4’) is well consistent with ‘G4EmDNAPhysics_option 5’ (hereinafter referred to as ‘option 5’); secondly, there are differences for the information of track structure and mean lineal energy between ‘option 2’ ‘option 4’ and ‘G4EmDNAPhysics_option 6’ (hereinafter referred to as ‘option 6’); thirdly, the influence of the model on the mean lineal energy decreases with the increase of the radius of the scoring spheres, whereas mean lineal energy increases as the tracking cut increases. Several alternative discrete physics constructors of Geant4-DNA are comprehensively discussed overlaying multiple perspectives under different conditions in this work.

Modeling of yield estimation for DNA strand breaks based on Monte Carlo simulations of electron track structure in liquid water

DNA strand breaks are induced in cells mainly composed of liquid water along ionizing radiation tracks. For estimating DNA strand break yields, track structures for electrons in liquid water in Monte Carlo simulations are of great importance; however, detailed simulations to obtain both energy deposition and free radical reaction to DNA are time-consuming processes. Here, we present a simple model for estimating yields of single- and double-strand breaks (SSB, DSB, and DSB/SSB ratio) based only on spatial patterns of inelastic interactions (i.e., ionization and electronic excitation) generated by electrons, which are evaluated by the track structure mode of Particle and Heavy Ion Transport code System without analyzing the production and diffusion of free radicals. In the present model, the number of events per track and that of a pair composed of two events within 3.4 nm (10 base pairs) were stochastically sampled for calculating SSB and DSB yields. The results calculated by this model agree well with other simulations and experimental data on the DSB yield and the DSB/SSB ratio for monoenergetic electron irradiation. This model also demonstrates the relative biological effectiveness at the DSB endpoint for various photon irradiations, indicating that the spatial pattern composed of ionization and electronic excitation without physicochemical and chemical stages is sufficient to obtain the impact of electrons on the initial DNA strand break induction.

Development of a new Geant4-DNA electron elastic scattering model for liquid-phase water using the ELSEPA code

This paper presents the calculation of new elastic scattering cross sections for the simulation of electron interactions in liquid water. The calculations are based on the “ELastic Scattering of Electrons and Positrons by neutral Atoms” code, which adopts a Dirac partial wave analysis. A Muffin-tin potential was used in order to account for the liquid-phase of water, and the optical parameters of the correlation-polarization and the inelastic absorption potentials were optimized against vapour-phase water data. The differential and total elastic scattering cross sections calculated in the present work show a global agreement with the experimental data. The impact of these elastic scattering cross sections on the transport of electrons in liquid water was evaluated by track-structure simulations of range, dose-point-kernel, microdosimetric spectra, and ionization clustering using the Geant4-DNA simulation toolkit. The results are compared against those obtained with the elastic scattering models already available in Geant4-DNA and are discussed.

Microdosimetry of electrons in liquid water using the low-energy models of Geant4

The biological effects of ionizing radiation at the cellular level are frequently studied using the well-known formalism of microdosimetry, which provides a quantitative description of the stochastic aspects of energy deposition in irradiated media. Energy deposition can be simulated using Monte Carlo codes, some adopting a computationally efficient condensed-history approach, while others follow a more detailed track-structure approach. In this work, we present the simulation of microdosimetry spectra and related quantities (frequency-mean and dose-mean lineal energies) for incident monoenergetic electrons (50 eV–10 keV) in spheres of liquid water with dimensions comparable to the size of biological targets: base pairs (2 nm diameter), nucleosomes (10 nm), chromatin fibres (30 nm) and chromosomes (300 nm). Simulations are performed using the condensed-history low-energy physics models (“Livermore” and “Penelope”) and the track-structure Geant4-DNA physics models, available in the Geant4 Monte Carlo simulation toolkit. The spectra are compared and the influence of simulation parameters and different physics models, with emphasis on recent developments, is discussed, underlining the suitability of Geant4-DNA models for microdosimetry simulations. It is further shown that with an appropriate choice of simulation parameters, condensed-history transport may yield reasonable results for sphere sizes as small as a few tens of a nanometer.

Monte Carlo Electron Track Structure Calculations in Liquid Water Using a New Model Dielectric Response Function.

Monte Carlo track structure codes provide valuable information for understanding radiation effects down to the DNA level, where experimental measurements are most difficult or unavailable. It is well recognized that the performance of such codes, especially at low energies and/or subcellular level, critically depends on the reliability of the interaction cross sections that are used as input in the simulation. For biological media such as liquid water, one of the most challenging issues is the role of condensed-phase effects. For inelastic scattering, such effects can be conveniently accounted for through the complex dielectric response function of the media. However, for this function to be useful it must fulfill some important sum rules and have a simple analytic form for arbitrary energy- and momentum-transfer. The Emfietzoglou-Cucinotta-Nikjoo (ECN) model offers a practical, self-consistent and fully analytic parameterization of the dielectric function of liquid water based on the best available experimental data. An important feature of the ECN model is that it includes, in a phenomenological manner, exchange and correlation effects among the screening electrons, thus, going beyond the random-phase approximation implicit in earlier models. In this work, inelastic cross sections beyond the plane wave Born approximation are calculated for low-energy electrons (10 eV-10 keV) based on the ECN model, and used for Monte Carlo track structure simulations of physical quantities relevant to the microdosimetry of low-energy electrons in liquid water. Important new developments in the physics of inelastic scattering are discussed and their effect on electron track structure is investigated by a comparison against simulations (under otherwise identical conditions) using the Born approximation and a simpler form of the dielectric function based on the Oak Ridge National Laboratory model. The results reveal that both the dielectric function and the corrections to the Born approximation may have a sizeable effect on track structure calculations at the nanometer scale (DNA level), where the details of inelastic scattering and the role of low-energy electrons are most critical.

Electronic Levels of Excess Electrons in Liquid Water.

We provide a consistent description of the electronic levels associated with localized and delocalized excess electrons in liquid water by combining hybrid-functional molecular dynamics simulations with a grand canonical formulation of solutes in aqueous solution. The excess electron localizes in a cavity with an average radius of 1.8 Å and a majority coordination of five water molecules. The vertical binding energy, the optical s-p transitions, and the adiabatic redox level are found to agree closely with their experimental counterparts. The energy level associated with electron delocalization V0 is inferred to lie at -0.97 eV with respect to the vacuum level.

On the reverse micelle effect in liquid scintillation counting

This work looks into the tracks of electrons in nanoemulsive scintillating media using the Monte Carlo Geant4-DNA code which simulates event-by-event interactions of electrons in liquid water down to the eV, without resorting to the condensed history method. It demonstrates that the average number of micelles in which electrons deposit energy is quite large, increasing with their emission energy, decreasing with micelle size, and rising with micelle concentration. The probability of an electron ending its track in a micelle is found to be rather large and micelle size-dependent below 1keV, and approximating the aqueous fraction at higher energies. Analyses of the Monte Carlo estimated energy depositions in the aqueous phase and in the scintillant tell of a micelle quenching effect, with the micelle size shaping the quenching at low energy and the micelle concentration governing it at higher energies. The micelle effect on the 3H and 63Ni beta spectra is discussed for a range of micelle sizes and concentrations. This paper also computes the ionisation quenching function using Birk's law whilst considering the full energy losses in the micelles bisecting the electron pathway, and not just that incurred in the primary micelle enclosing the decaying nuclide. The ionisation quenching function is then used to calculate the detection efficiencies for 3H, 63Ni, 54Mn and 55Fe. The effect of the micelle size is found to be small for beta emitters but significant for the electron capture nuclides. TDCR measurements of 63Ni samples covering 8 aqueous fractions are analysed with and without explicit treatment of the micelle effect. Activities in the two representations agree within 0.02%. The ratios of the corresponding figures of merit are found to coincide with the scintillant fractions.