On the lifetimes and physical nature of incompletely relaxed electrons in liquid water

Despite intense study over the past two decades, the dynamics of electron solvation in water, particularly regarding the physical properties and lifetimes of non-equilibrium, incompletely relaxed electrons, remain very controversial. Both experimental and theoretical studies have reported a very diverse range, from approximately 50 to approximately 1000 fs, for the lifetime of the p-like excited state of the hydrated electron, and the nature of incompletely relaxed states remains unclear. Here, we reveal that these controversies are to a great extent due to a hidden effect, i.e., the universal existence of a coherence spike at delay time zero in pump-probe spectroscopic kinetics traces. After removing this spike effect, we show that the intrinsic lifetimes of the two incompletely relaxed states in bulk water are 180+/-30 and 545+/-30 fs, respectively. Moreover, our results using iododeoxyuridine as a molecular probe reveal that both states are electronically excited states of the hydrated electron and the second state of a 545 fs lifetime is the long-sought wet electron. These results resolve the long-standing controversies about electron hydration dynamics.     

Hydrated electron extinction coefficient revisited

The extinction coefficient of the hydrated electron (e(-))aq generated by pulse radiolysis is evaluated relative to the methyl viologen radical cation (*)MV(+), whose extinction coefficient at 605 nm has been carefully measured in the past. We find that the room temperature (e(-))aq extinction coefficients reported in the literature are underestimated by 10-20%. We obtain = 22,700 M(-1) cm(-1) for the 20 degrees C hydrated electron at 720 nm, assuming the (*)MV(+) extinction is 13,700 M(-1) cm(-1) at 605 nm. This has implications both for second-order reaction rate measurements of (e(-))aq and for the estimate of its integrated oscillator strength.     

Molar absorption coefficient of pyrene aggregates in water

The molar absorption coefficient of pyrene aggregates, epsilon(E0), was determined for a series of pyrene-labeled poly(N,N-dimethylacrylamide)s (Py-PDMA) having different pyrene contents. Aqueous solutions of Py-PDMA having pyrene contents ranging from 263 to 645 mumol of pyrene per gram of polymer were studied by UV-vis absorbance and time-resolved fluorescence spectroscopy. The global analysis of the monomer and excimer fluorescence decays with the fluorescence blob model yielded the fractions of the overall absorption contributed by all the pyrene species present in solution. The combined knowledge of the fractions obtained from the global analysis of the time-resolved fluorescence decays, the total absorption of the Py-PDMA solution obtained from UV-vis spectroscopy, and the total pyrene concentration in the solution obtained from the known pyrene content of each Py-PDMA sample led to the determination of the molar absorption coefficient of pyrene aggregates. Regardless of the pyrene content of the Py-PDMA samples and hence the level of association of the pyrene pendants in solution, all Py-PDMA samples yielded similar epsilon(E0) values over the range of wavelengths studied, namely, from 325 to 350 nm. The averaged epsilon(E0) was found to be red-shifted relative to unassociated pyrenes by 3 nm as well as having a value at the 0-0 peak of 21 000 M(-1).cm(-1) reduced from 34 700 M(-1).cm(-1) for unassociated pyrenes. The determination of epsilon(E0) enabled the first determination of the absolute fraction of associated pyrenes for aqueous solutions of a series of pyrene-labeled water-soluble polymers. The procedure outlined in this study is applicable to any pyrene-labeled water-soluble polymer and provides a new means to study quantitatively the effect of the hydrophilic-to-lipophilic balance on the hydrophobic associations generated by hydrophobically modified water-soluble polymers. As an application, the average number of pyrenes involved in a pyrene aggregate generated by Py-PDMA in water is determined.     

Molar excess Gibbs free energies of mixtures of ethanolamines and water

Thermodynamic information about the vapor—liquid equilibria of systems containing water and ethanolamines is needed in the design and optimization of important industrial processes. This knowledge is also useful in the investigation of some phenomena such as the thermal conversion of ethanolamines or their complexation reactions with metals.Physico-chemical investigations involving aqueous solutions of ethanolamines are scarce, and sometimes contradictory, in the literature. It has been stated [1] that the system diethanolamine—water obeys Raoult's law. However, there have been studies [2] indicating departure from ideal behavior for this system.The purpose of this work was to determine the molar excess Gibbs free energies of the systems formed by water and the ethanolamines.     

Calculations of the pseudopotential for the excess electron in water and methane

The potentials for excess electrons in cavities of water and methane are analyzed with the use of the pseudopotential theory. The results are consistent with the previous discussions; the excess electron in water can probably be trapped in the cavity and that in methane will be quasifree. In the case of methane, the effect of the molecular coordination on the potential is further discussed by varying the cavity radius.     

The birefringence and extinction coefficient of positive and negative liquid crystals in the terahertz range

Birefringence and extinction coefficients of positive nematic liquid crystal (NLC) MLC-2142 and negative NLC BHR28000-400 are measured by terahertz time-domain spectroscopy system (THz-TDS). Frequency ranging from 0.1 to 0.6 THz, the birefringence of positive NLC MLC-2142 increases with the increase of frequency, and keeps larger than 0.23, which exhibits application potential in tunable broadband LC THz device where a large birefringence is required. In contrast, the birefringence of BHR28000-400 decreases with the increased frequency, which shows a completely different optical property from the positive NLC. The extinction coefficient of the above two kinds of liquid crystals are also investigated.     

Conjecture on electron trapping in liquid water

From the available experimental and theoretical evidence it appears reasonably certain that electron thermalization precedes trapping in liquid water. The vast majority of prospective trapping sites do not actually bind an electron permanently due to insufficient attractive “strength”, but scatter the thermalized electron after going through a state of temporary negative ion formation. Trapping probably occurs efficiently over a relatively narrow range of trapping potentials just sufficient to bind the electron. The 10^-13 s time scale appears to be very important in liquid water, being dominated by energy loss of epithermal electrons, trapping and eventual solvation.     

Molar extinction coefficients of some commonly used solvents

Molar extinction coefficients of some commonly used solvents (ethanol (C₂H₅OH), methanol (CH₃OH), propanol (C₃H₇OH), butanol (C₄H₉OH), water (H₂O), toluene (C₇H₈), benzene (C₆H₆), carbontetrachloride (CCl₄), acetonitrile (C₄H₃N), chlorobenzene (C₆H₅Cl), diethylether (C₄H₁₀O) and dioxane (C₄H₈O₂)) have been determined by a well-collimated narrow beam transmission geometry at 279, 356, 662, 1173, 1252 and 1332 keV γ rays. The total γ ray interaction cross sections of these solvents have also been determined. A good agreement has been obtained between the experimental results with the theoretical values evaluated through XCOM calculations.     

Origin of the magic numbers of water clusters with an excess electron

Electron-bound water clusters [e(-)(H(2)O)(n)] show very strong peaks in mass spectra for n=2, 6, 7, and (11), which are called magic numbers. The origin of the magic numbers has been an enigma for the last two decades. Although the magic numbers have often been conjectured to arise from the intrinsic properties of electron-bound water clusters, we attributed them not to their intrinsic properties but to the particularly weak stability of the corresponding neutral water clusters (H(2)O)(n=2,6,7, and (11)). As the cluster size increases; this nonsmooth characteristic feature in stability of neutral water clusters is contrasted to the smooth increase in stability of e(-)-water clusters. As the magic number clusters have significant positive adiabatic electron affinities, their abundant distributions in atmosphere could play a significant role in atmospheric thermodynamics.     

Molar excess volumes of ternary mixtures of nonelectrolytes

Molar excess volumes V^E_ijk of methylenebromide i + pyridine j + β-picoline (k, cyclohexane (i) + pyridine (j) + β-picoline(K), benzene(i)+toluene(j)+1,2-dichloroethane(k), benzene(i) + 0-xylene(j) + 1,2-dichloroethane(k) and benzene(i) + p-xylene(j) + 1,2-dichloroethane(k) mixtures have been determined dilatometrically at 298.15 K. The data have been examined in terms of Sanchez and Lacombe theory and the graph-theoretical approach, and it is found that they are described well by the latter. Self- and cross-volume interaction coefficients V_jk, V_jjk and V_jkk, etc., have also been evaluated and the values utilised to study molecular interactions between the jth and kth molecular species in the presence of the ith in these i + j + k mixtures.     

Molar absorption coefficient of ozone in aqueous solutions

The value of the molar absorption coefficient of ozone in aqueous solutions (2992 ± 71 M^–1 cm^–1 at 260 nm) is found based on the determination of ozone concentration by iodometry. This value is confirmed by the results of determination of O₃ concentration by reaction with the bromide ion and virtually coincides with the maximum absorption coefficient of ozone in the gas phase in the region the Hartley band. In the determinations of ozone concentration in aqueous solutions by direct spectrophotometry, we recommend the value of the molar absorption coefficient ε(О₃)₂₆₀ = 3000 M^–1 cm^–1.     

Molar excess enthalpies of ternary mixtures of non-electrolytes

Molar excess enthalpies, H^E_ijk(T₁, x_i, x_j), for methylenebromide (i)+pyridine (j)+β-picoline (k); pyridine (i)+β-picoline (j)+cyclohexane (k); benzene (i)+toluene (j)+1,2-dichloroethane (k); benzene (i)+o-xylene (j)+1,2-dichloroethane (k); and benzene (i)+p-xylene (j)+1,2-dichloroethane (k) mixtures have been measured calorimetrically as a function of temperature and composition. The data have been analysed in terms of the Sanchez and Lacombe theory and using an approach employing the “graph theoretical” concept of connectivity parameters to characterize its pure components. It has been observed that the H^E_ijk (T, x_i, x_j) data calculated from the “graph theoretical” approach using ³ξ values based on δ^v considerations (that take into consideration the valency of individual atoms of the molecular graph constituent components) best reproduces the corresponding experimental H^E_ijk data.     

Molar extinction coefficients in aqueous solutions of some amino acids

Mass attenuation coefficients of amino acids viz. glycine (C₂H₅NO₂), l-Serine (C₃H₇NO₃), l-Theronine (C₄H₉NO₃), l-Proline (C₅H₉NO₂), l-Valine (C₅H₁₁NO₂) and l-Phenylalanine (C₉H₁₁NO₂) in aqueous solutions have been determined at 81, 356, 511, 662, 1173 and 1332 keV by the gamma-ray transmission method in a narrow beam good geometry setup. Precisely measured densities of these solutions were used for the determination of these coefficients which varied systematically with the corresponding changes in the concentrations (g/cm³) of the solutions. Molar extinction coefficients of amino acids were then obtained at these energies and were found to be in good agreement with the theoretical results. In addition, total interaction cross sections of amino acids in aqueous solutions were also calculated.     

Molar excess volumes and molar excess enthalpies of methylenebromide + aromatic hydrocarbon mixtures

Molar excess volumes V^e and molar excess enthalpies H^e of binary methylenebromide (i) +benzene. +toluene, and + o^?, + m^? and + p-xylene (j) mixtures have been determined at 298.15 and 308.15 K. The data have been analysed in terms of recent approaches for solutions of nonelectrolytes, and the results suggest that these mixtures are characterised by specific interactions between the components. Self-volume interaction coefficients V_iiV_jj have also been evaluated.     

Molecular interactions in binary mixtures of non-electrolytes: Molar excess enthalpies

Molar excess enthalpies, H^E, for pyridine (i) + α-picoline (j), + β-picoline (j), + γ-picoline (j); pyridine (i) + cyclohexane (j); β-picoline (i) + cyclohexane (j); methylenebromide (i) + pyridine (j), + β-picoline (j) mixtures have been measured calorimetrically as a function of temperature and composition. The H^E data at 298.15 and 308.15 K have been analysed in terms of the Sanchez and Lacombe theory and the “graph theoretical approach”. The graph theoretical approach describes the H^E data well for all these mixtures. This approach has been critically examined and it is found to provide an insight into the nature of molecular interactions between the components of these mixtures. NMR studies on methylene bromide (i) + β-picoline (j) andβ-picoline (i) + pyridine (j) further support these conclusions.     

Topological and thermodynamic investigations of molecular interactions in binary mixtures: Molar excess volumes and molar excess enthalpies

Molar excess volumes and molar excess enthalpies of butyl acetate (i) with cyclohexane or benzene or toluene or o-, m- or p-xylene (j) binary mixtures have been measured dilatometrically and calorimetrically over the entire composition range at 308.15 K. The observed data have also been analyzed in terms of graph theoretical approach. The analysis of V^E data by graph theoretical approach suggests that butyl acetate in pure state exists as associated entity and (i + j) mixtures are characterized by the presence of (i–j) molecular entity. It has further been observed that V^E and H^E values calculated by this approach agree well with the corresponding experimental values. The presence of molecular entity is further confirmed by IR study of (i + j) mixture.     

Statistical mechanics of hydrated electron recombination in liquid and supercritical water

The photochemical yield of hydrated electrons as a function of temperature in liquid and supercritical water is treated in terms of energy fluctuations of the medium. The geminate pair, consisting of a positive ion and a hydrated electron, is regarded as a H-like atom embedded in a completely relaxed dielectric continuum. If the local medium energy is larger than the ionization energy of this atom, the electron escapes its geminate partner. By making use of the classical theory of energy fluctuations, escape probability is described by a simple explicit function, the variable of which is a combination of temperature, relative permittivity, and specific heat. First our earlier calculations on the recombination of solvated electrons, produced by ionizing radiation in a number of polar liquids, are improved and then the theory is compared with the experimental results on temperature dependent electron survival by Kratz et al. [S. Kratz, J. Torres-Alcan, J. Urbanek, J. Lindner, and P. Vo?hringer, Phys. Chem. Chem. Phys. 12, 12169 (2010)]. Two adjustable parameters are needed to achieve reasonable quantitative agreement.     

Thermodynamics of molecular interactions in binary mixtures of non-electrolytes. Molar excess volumes

Molar excess volumes, V^E, for pyridine (A) + α-picoline (B), + β-picoline (B) and + γ-picoline (B) and benzene (A) + toluene (B), + o-xylene (B) and + p-xylene (B) and carbon tetrachloride (A) + n-heptane (B) have been measured dilatometrically as a function of temperature and composition and have been utilized to study B—B and B—B—B interactions in the presence of A via the Mayer—McMillan approach. A model has also been presented to account for these B—B and B—B—B interactions. The V^E data at 308.15 K have also been analysed in terms of the “graph theoretical” approach which describes the V^E data well for all these mixtures at 308.15 K. The “graph theoretical” approach has further been extended to successfully evaluate V^E data for a mixture at any temperature, T₂, when the V^E data at T₁ are known.