Absorption Spectrum Of Solvated Electron Research Articles

Direct Observation of Solvated Electrons in Deep Eutectic Solvents: Efficient Capture of Presolvated Electrons by DNA Base.

The solvated electron being the simplest form of an extremely reactive intermediate is of great fundamental interest in chemistry, physics, and biology since its discovery. Recently, deep eutectic solvents (DESs) have been in focus as biodegradable and cost-effective alternative to ionic liquids (ILs) for different applications. These include areas where electron transport and transfer processes are involved. Herein, we present the first report on the existence, yield, and properties of solvated electrons in three deep eutectic solvents, reline, ethaline, and glyceline, composed of choline chloride as a hydrogen bond acceptor and urea, ethylene glycol, and glycerol (Gly) as hydrogen bond donors, respectively, at a molar ratio of 1:2. The varied transient absorption spectra of solvated electrons in these DESs have been explained on the basis of polarity, hydrogen-bonding effect, and the moieties responsible for creating the environment for solvation. The yield and average lifetime follow the trends in viscosity as well as the reactivity of electrons with the components. The C37 value, a measure of the efficiency of scavenging presolvated electrons, is the highest in ethaline in the case of nitrate ions, which indicates the slowest solvation process in this DES. The presolvated electron capture by a DNA base, an aspect considered to be important in cancer radiotherapy, could be monitored conveniently in these liquids at a much longer time scale compared to that reported in aqueous solutions. Bimolecular rate constants for the reaction of solvated electrons with nitrate and the DNA base have been calculated and compared in the three DESs. Unlike in ILs, these experimentally obtained values are comparable to the diffusion-controlled rate constants in DESs.

ChemInform Abstract: Absorption Spectra of Solvated Electrons and Radicals Observed in the Pulse Radiolysis of Cis and Trans Isomers of Methylcyclohexanols and Cyclopentanol to Cyclooctanol.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Solvated electrons at elevated temperatures in different alcohols: Temperature and molecular structure effects

The absorption spectra of solvated electrons in pentanol, hexanol and octanol are measured from 22 to 200, 22 to 175 and 50 to150 °C, respectively, at a fixed pressure of 15 MPa, using nanosecond pulse radiolysis technique. The results show that the peak positions of the absorption spectra have a red-shift (shift to longer wavelengths) as temperature increases, similar to water and other alcohols. Including the above mentioned data, a compilation of currently available experimental data on the energy of absorption maximum ( E max) of solvated electrons changed with temperature in monohydric alcohols, diols and triol is presented. E max of solvated electron is larger in those alcohols that have more OH groups at all the temperatures. The molecular structure effect, including OH numbers, OH position and carbon chain length, is investigated. For the primary alcohols with same OH group number and position, the temperature coefficient increases with increase in chain length. For the alcohols with same chain length and OH numbers, temperature coefficient is larger for the symmetric alcohols than the asymmetric ones.

The nanoheterogeneous structure of aqueous solutions of n-propanol

The results of positron spectroscopy and molecular light scattering studies, the data on radiationchemical yields and optical absorption spectra of solvated electrons formed under the action of ionizing radiation, and the data on the concentration dependences of viscosity, adiabatic compressibility, the velocity of sound, and partial molar volume were used to determine the structure of water-n-propanol mixtures. The conclusion was drawn that the insertion of alcohol molecules into water network voids over the range of alcohol mole fractions 0 x2 > 0.9), its molecules combined into nanodrops.

A theory of elementary photophysical processes with the participation of excess electrons in polar liquids

The main concepts of the new theory of processes with the participation of excess electrons in polar liquids are considered. The theory takes into account that (1) polar liquids are electrostatically inhomogeneous (local potentials on molecules are different) and (2) a molecule can accept an electron for a short time to produce an anion in an unstable state with a certain energy and lifetime. A discrete model of a substance consisting of molecules with constant dipole moments is used. Excess electrons in a liquid are described by energy distribution density, and the behavior of electrons, by quantum mechanics equations. The experimental data on the photoionization of water and aqueous solutions of salts and the low threshold energy of photons (∼6.5 eV) at which solvated electrons appear in water are explained. The absorption spectra of water with excess electrons at the first and subsequent time moments after their photogeneration are reproduced theoretically. The dependence of the photoemission of solvated electrons from potassium-ammonia solutions on the energy of photons is interpreted. The continuous spectrum of spontaneous radiation of solvated electrons in liquid ammonia and water is calculated. The optical absorption spectra of solvated electrons in such polar liquids as water and ammonia are reproduced.

Effect of temperature on the absorption spectra of the solvated electron in 1-propanol and 2-propanol: Pulse radiolysis and laser photolysis studies at temperatures up to supercritical condition

The absorption spectra of solvated electrons in 1-propanol and 2-propanol have been investigated from 22 to 270 °C at a fixed pressure of 7 MPa, by using both nanosecond pulse radiolysis and laser photolysis techniques. The results show that, even up to supercritical conditions, it is still possible to measure unambiguously the absorption spectra of solvated electron in these two propanols. The peak positions of the absorption spectra show a red-shift (shifts to longer wavelengths) as temperature increases, similar to water and other alcohols, but the temperature efficiency, d E max/d T, of 1-propanol is larger than that of 2-propanol. In addition, in clear contrast to that of pulse radiolysis, in laser photolysis experiments, an increase in the maximum absorbance of the absorption spectra of solvated electron with temperature up to ∼200 °C is attributed to the increase of absorbance (CTTS absorption band) of I − anion at 248 nm with increasing temperature.

One-photon photodetachment of I− in glycerol: Spectra and yield of solvated electrons in the temperature range 329⩽T⩽536K

Solvated electrons in glycerol were generated via a resonant one-photon photodetachment of the charge-transfer-to-solvent (CTTS) band of I- in glycerol (Gl) after irradiation with a 248 nm excimer laser. Optical absorption spectra of solvated electrons (esolv-) in Gl were recorded as a function of temperature (381<or=T<or=505 K). The observed redshift of the absorption maximum, homegamax, yields a temperature coefficient d(homegamax)/dT=-(2.67+/-0.07)x10(-3) eV K-1. For solutions with a concentration c(I-) approximately 10(-3)M, the absorbance of esolv- at homegamax increases by a factor of about 65 when the temperature is raised from 329 to 536 K. This effect can be partially explained by a temperature-dependent redshift of the CTTS spectrum of I- in Gl with respect to the laser wavelength. The main contribution to the increasing yield of esolv- is determined by diffusion controlled escape dynamics of the electron in the contact pair (I:e-)solv which is formed very fast during the detachment process. At room temperature no absorption of esolv- (absorbance<1.0x10(-3)) could be observed which is probably a result of an extremely small self-diffusion coefficient of Gl (a factor of 1250 lower than that of water at 298 K). The results are compared with a previous study of I- in ethylene glycol.

The role of solvent structure in the absorption spectrum of solvated electrons: Mixed quantum/classical simulations in tetrahydrofuran

In polar fluids such as water and methanol, the peak of the solvated electron's absorption spectrum in the red has been assigned as a sum of transitions between an s-like ground state and three nearly degenerate p-like excited states bound in a quasispherical cavity. In contrast, in weakly polar solvents such as tetrahydrofuran (THF), the solvated electron has an absorption spectrum that peaks in the mid-infrared, but no definitive assignment has been offered about the origins of the spectrum or the underlying structure. In this paper, we present the results of adiabatic mixed quantum/classical molecular dynamic simulations of the solvated electron in THF, and provide a detailed explanation of the THF-solvated electron's absorption spectrum and electronic structure. Using a classical solvent model and a fully quantum mechanical excess electron, our simulations show that although the ground and first excited states are bound in a quasispherical cavity, a multitude of other, nearby solvent cavities support numerous, nearly degenerate, bound excited states that have little Franck-Condon overlap with the ground state. We show that these solvent cavities, which are partially polarized so that they act as electron trapping sites, are an inherent property of the way THF molecules pack in the liquid. The absorption spectrum is thus assigned to a sum of bound-to-bound transitions between a localized ground state and multiple disjoint excited states scattered throughout the fluid. Furthermore, we find that the usual spherical harmonic labels (e.g., s-like, p-like) are not good descriptors of the excited-state wave functions of the solvated electron in THF. Our observation of multiple disjoint excited states is consistent with femtosecond pump-probe experiments in the literature that suggest that photoexcitation of solvated electrons in THF causes them to relocalize into solvent cavities far from where they originated.

Is there any Correlation between the Mobility and the Absorption Spectra of Solvated Electrons in Polar Solvents?

Some years ago Jay-Gerin and Ferradini attempted to establish a correlation between the optical absorption spectrum and the mobility of excess electrons in various polar solvents (J. Chem. Phys.

Optical Absorption of Solvated Electrons in Water and Tetrahydrofuran/Water Mixtures

In the past Jou and Dorfman (J. Chem. Phys. 1973, 58, 4715) have determined the optical absorption spectra of solvated electrons (esolv-) in binary mixtures of tetrahydrofuran (THF) and water over the entire concentration range. From these experiments they concluded that the position of the absorption maximum and the width at half-height of the band are dominated by water. By additional experiments we show that at least for some mixtures with a mole fraction X(THF) ≤ 0.50, we obtain spectra at 298 K which agree almost completely with those of esolv- in pure water at elevated temperatures obtained by Jou and Freeman (J. Phys. Chem. 1979, 83, 2383). It follows that for this range of composition, excess electrons are obviously hydrated and the large amount of THF of up to X(THF) = 0.49 changes the water structure of the hydrated electron only slightly. The same effect can be produced by a temperature increase of T = 80 K in pure water. From the spectra we have determined equilibrium ground-state properties o...

Article

The energy and asymmetry of the optical absorption spectrum of solvated electrons, es- , change in a nonlinear fashion on changing the solvent through the series HOH, CH3OH, CH3CH3OH, (CH3)2CHOH, (CH3)3COH. The ultimate, quantum-statistical mechanical, interpretation of solvated electron spectra is needed to describe the solvent dependence. The previously reported optical spectrum of es- in tert-butanol was somewhat inaccurate, due to a small amount of water in the alcohol and to limitations of the infrared light detector. The present note records the remeasured spectrum and its temperature dependence. The value of the energy at the absorption maximum (EAmax) is 155 zJ (0.97 eV) at 299 K and 112 zJ (0.70 eV) at 338 K; the corresponding values of G epsilon max (10-22 m2 aJ-1) are 1.06 and 0.74. These unusually large changes are attributed to the abnormally rapid decrease of dielectric permittivity of tert-butanol with increasing temperature. The band asymmetry at 299 K is Wb/Wr = 1.8.Key words: optical absorption spectrum, solvated electron, solvent effects, tert-butanol, temperature dependence.

Optical absorption spectrum of solvated electrons in pure &lt;i&gt;tert&lt;/i&gt;-butanol: effect of temperature

The energy and asymmetry of the optical absorption spectrum of solvated electrons, es, change in a nonlinear fashion on changing the solvent through the series HOH, CH3OH, CH3CH3OH, (CH3)2CHOH, (CH3)3COH. The ultimate, quantum-statistical mechanical, interpretation of solvated electron spectra is needed to describe the solvent dependence. The previously reported optical spectrum of es − in tert-butanol was somewhat inaccurate, due to a small amount of water in the alcohol and to limitations of the infrared light detector. The present note records the remeasured spectrum and its temperature dependence. The value of the energy at the absorption maximum (EAmax) is 155 zJ (0.97 eV) at 299 K and 112 zJ (0.70 eV) at 338 K; the corresponding values of Gemax (10 m aJ) are 1.06 and 0.74. These unusually large changes are attributed to the abnormally rapid decrease of dielectric permittivity of tert-butanol with increasing temperature. The band asymmetry at 299 K is Wb/Wr = 1.8.

Optical absorption spectra of solvated electrons in 1-butylamine–water mixed solvents

The optical absorption spectra of es− in 1-butylamine–water mixed solvents increase smoothly in energy and intensity as the water content is increased, with the exception of a small decrease in intensity on going from 95 to 100 mol% water. At 298 K the value of Gεmax increases from 1.42 × 10−21 m2/16 aJ (8.6 × 103 es−L/100 eV mol cm) in pure 1-butylamine to 8.3 × 10−21 m2/16 aJ (50 × 103 es−L/100 eV mol cm) in pure water, and the value of EAmax increases from 115 zJ (0.72 eV) to 278 zJ (1.74 eV). In the pure amine, if G(es−) = 0.27, then εmax = 5.3 × 10−21 m2/es− (3200 m2/mol). The solvent composition dependences of Gεmax and EAmax indicate little selective solvation of es− by water; this might be due to relatively "ideal" mixing of water and amine in the binary solvents. The temperature coefficient −dEAmax/dT = 0.43 zJ/K in pure 1-butylamine, 0.47 in pure water, and has a minimum of 0.27 in the 50:50 mixture. Keywords: 1-butylamine–water mixed solvents, optical absorption spectra, solvated electron, temperature dependence.

Temperature Dependence of Optical Absorption Spectra of Solvated Electrons in CD3OD for T .ltoreq. Tc

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTemperature Dependence of Optical Absorption Spectra of Solvated Electrons in CD3OD for T .ltoreq. TcV. Herrmann and P. KrebsCite this: J. Phys. Chem. 1995, 99, 18, 6794–6800Publication Date (Print):May 1, 1995Publication History Published online1 May 2002Published inissue 1 May 1995https://doi.org/10.1021/j100018a007RIGHTS & PERMISSIONSArticle Views112Altmetric-Citations28LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (2 MB) Get e-Alerts

Spectroscopic properties of the solvated electron in water, alcohols, amines, ethers and alkanes

The near-IR and visible absorption spectra of solvated electrons in water, alcohols, amines, ethers and alkanes were calculated in terms of the electron-vibron coupling and compared with experiment. The role of the H-bond is discussed.

Absorption spectra of solvated electrons and radicals observed in the pulse radiolysis of cis and trans isomers of methylcyclohexanols and cyclopentanol to cyclooctanol

The absorption spectra of solvated electrons have been determined in cis and trans isomers of 2-, 3-, and 4-methylcyclohexanol, cyclopentanol through cyclooctanol, and some other alcohols by microsecond pulse radiolysis at room temperature. With the methylcyclohexanols the wavelength at the absorption maximum, {lambda}{sub max}(e{sub s}{sup {minus}}), of solvated electrons for the cis isomer is different from that for the trans isomer by about 100nm, irrespective of the position where a hydrogen atom on the cyclohexanol ring is substituted for a methyl group. It is inferred from the conformational analysis of the methylcyclohexanols that {lambda}{sub max}(e{sub s}{sup {minus}}) for solvated electrons surrounded by the equatorial OH groups is observed at shorter wavelength than that surrounded by the axial OH groups. The optical spectra due to radicals have also been measured in all alcohols studied except tert-butyl alcohol.

Search for Urbach tails in the optical absorption spectra of solvated electrons in alcohols and water

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSearch for Urbach tails in the optical absorption spectra of solvated electrons in alcohols and waterC. Houee-Levin, C. Tannous, and J. P. Jay-GerinCite this: J. Phys. Chem. 1989, 93, 20, 7074–7077Publication Date (Print):October 1, 1989Publication History Published online1 May 2002Published inissue 1 October 1989https://doi.org/10.1021/j100357a012RIGHTS & PERMISSIONSArticle Views131Altmetric-Citations13LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (466 KB) Get e-Alerts

The nature of the transitions comprising the optical absorption spectra of solvated electrons

The theory of photoejection spectra of molecular anions is adapted for application to analyses of optical absorption data of solvated electrons in a number of different solvents. The results obtained generally support the identification of solvated electron optical absorption spectra entirely as bands of bound-to-continuum transitions and not as bound-to-bound transitions. Analyses of the absorbance behavior near the threshold for absorption lead to the conclusion that the solvated electron ground state deviates appreciably from spherical symmetry. Alternatively, the solvated electron ground state in ND 3 may be nearly spherically symmetric with a thermally accessible excited state of lower symmetry.

Effect of added salt on the optical absorption spectra of solvated electrons in liquid ammonia

Effect of added salt on the optical absorption spectra of solvated electrons in liquid ammonia

Optical indications of heterogeneous distribution of equilibrated solvated electrons in liquid and glassy ammonia-methanol solutions

Optical absorption spectra of solvated electrons, e − s, have been studied in methanol solutions of ammonia (12 and 16 m%) by pulse microsecond radiolysis. A jump of 0.7 eV has been found in the temperature dependencies of the energy of the optical absorption maximum, ( E − M), at the range 10–15°. The absorption bands showed a structured shape at the temperatures near the jump region. The enhanced photosensibility of the shape and the location of spectra of trapped electrons (e − t) has been discovered in these matrices at 77 K. The obtained results indicated that the equilibrated distribution of excess electrons over traps has common heterogeneous nature for the liquid and glassy ammonia-methanol mixture. Validity of the extension of this conclusion over other polar liquids is discussed.