arXiv subjects

I. A. Shkrob

Publications and source records attributed to I. A. Shkrob.

7 recordsLinked to original sources

arXiv2016

Dark Matter Search Results from the PICO-60 CF$_3$I Bubble Chamber

New data are reported from the operation of the PICO-60 dark matter detector, a bubble chamber filled with 36.8 kg of CF$_3$I and located in the SNOLAB underground laboratory. PICO-60 is the largest bubble chamber to search for dark matter to date. With an analyzed exposure of 92.8 livedays, PICO-60 exhibits the same excellent background rejection observed in smaller bubble chambers. Alpha decays in PICO-60 exhibit frequency-dependent acoustic calorimetry, similar but not identical to that reported recently in a C$_3$F$_8$ bubble chamber. PICO-60 also observes a large population of unknown background events, exhibiting acoustic, spatial, and timing behaviors inconsistent with those expected from a dark matter signal. These behaviors allow for analysis cuts to remove all background events while retaining $48.2\%$ of the exposure. Stringent limits on weakly interacting massive particles interacting via spin-dependent proton and spin-independent processes are set, and most interpretations of the DAMA/LIBRA modulation signal as dark matter interacting with iodine nuclei are ruled out.

hep-ex↗

arXiv2007

The structure and dynamics of solvated electron in polar liquids

A review with 106 references of the recent advances in understanding the structure, dynamics, and photodynamics of solvated electrons in polar liquids (and, to some degree, clusters): water, alcohols, ammonia, ethers. Both the orthodox (cavity) and heterodox (multimer anion) pictures of the solvated electron are discussed.

physics.chem-ph↗

arXiv2006

The Structure of Hydrated Electron. Part 1. Magnetic Resonance of Internally Trapping Water Anions: A Density Functional Theory Study

Density functional theory (DFT) is used to rationalize magnetic parameters of hydrated electron trapped in alkaline glasses as observed using Electron Paramagnetic Resonance (EPR) and Electron Spin Echo Envelope Modulation (ESEEM) spectroscopies. To this end, model water cluster anions (n=4-8 and n=20,24) that localize the electron internally are examined. It is shown that EPR parameters of such water anions (such as hyperfine coupling tensors of H/D nuclei in the water molecules) are defined mainly by the cavity size and the coordination number of the electron; the water molecules in the second solvation shell play a relatively minor role. An idealized model of hydrated electron (that is usually attributed to L. Kevan) in which six hydroxyl groups arranged in an octahedral pattern point towards the common center is shown to provide the closest match to the experimental parameters, such as isotropic and anisotropic hyperfine coupling constants for the protons (estimated from ESEEM), the second moment of the EPR spectra, and the radius of gyration. The salient feature of these DFT models is the significant transfer (10-20%) of spin density into the frontal O 2p orbitals of water molecules. Spin bond polarization involving these oxygen orbitals accounts for small, negative hyperfine coupling constants for protons in hydroxyl groups that form the electron-trapping cavity. In Part 2, these results are generalized for more realistic geometries of core anions obtained using a dynamic one-electron mixed qunatum/classical molecular dynamics model.

physics.gen-ph↗

arXiv2005

Ammoniated electron as a solvent stabilized multimer radical anion

The excess electron in liquid ammonia ("ammoniated electron") is commonly viewed as a cavity electron in which the s-type wave function fills the interstitial void between 6-9 ammonia molecules. Here we examine an alternative model in which the ammoniated electron is regarded as a solvent stabilized multimer radical anion, as was originally suggested by Symons [Chem. Soc. Rev. 1976, 5, 337]. In this model, most of the excess electron density resides in the frontier orbitals of N atoms in the ammonia molecules forming the solvation cavity; a fraction of this spin density is transferred to the molecules in the second solvation shell. The cavity is formed due to the repulsion between negatively charged solvent molecules. Using density functional theory calculations for small ammonia cluster anions in the gas phase, it is demonstrated that such core anions would semi-quantitatively account for the observed pattern of Knight shifts for 1-H and 14-N nuclei observed by NMR spectroscopy and the downshifted stretching and bending modes observed by infrared spectroscopy. It is speculated that the excess electrons in other aprotic solvents (but not in water and alcohols) might be, in this respect, analogous to the ammoniated electron, with substantial transfer of the spin density into the frontier N and C orbitals of methyl, amino, and amide groups forming the solvation cavity.

physics.chem-ph↗

arXiv2005

Geminate recombination of hydroxyl radicals generated in 200 nm photodissociation of aqueous hydrogen peroxide

The picosecond dynamics of hydroxyl radicals generated in 200 nm photoinduced dissociation of aqueous hydrogen peroxide have been observed through their transient absorbance at 266 nm. It is shown that these kinetics are nearly exponential, with a decay time of ca. 30 ps. The prompt quantum yield for the decomposition of H2O2 is 0.56, and the fraction of hydroxyl radicals escaping from the solvent cage to the water bulk is 64-68%. These recombination kinetics suggest strong caging of the geminate hydroxyl radicals by water. Phenomenologically, these kinetics may be rationalized in terms of the diffusion of hydroxide radicals out of a shallow potential well (a solvent cage) with an Onsager radius of 0.24 nm.

physics.chem-ph↗

arXiv2004

Hole Scavenging and Photo-Stimulated Recombination of Electron-Hole Pairs in Aqueous TiO2 Nanoparticles

It is shown that 532 nm and 1064 nm laser photoexcitation of trapped electrons generated by 355 nm photolysis of aqueous titania (TiO2) nanoparticles causes rapid photobleaching of their absorbance band in the visible and near IR. This photobleaching occurs within the duration of the laser pulse (3 ns FWHM); it is caused by photoinduced electron detrapping followed by rapid recombination of the resulting free electron and a trapped hole. The quantum yield for the electron photobleaching is ca. 0.28 for 532 nm and ca. 0.024 for 1064 nm photoexcitation. Complete separation of the spectral contributions from trapped electron and hole is demonstrated using glycerol as a selective hole scavenger. When glycerol is added to the solution, some light-absorbing holes are scavenged promptly within the duration of the 355 nm photoexcitation pulse, some are scavenged at a slower rate over the first 200 ns after the 355 nm pulse, and the rest are not scavenged, even at high concentration of the scavenger (> 10 vol %). A reaction with chemi- and physi- sorbed glycerol would account for the prompt and the slow hole decay, respectively. The implications of these results are discussed.

physics.chem-ph↗

arXiv2004

Efficient, rapid one-electron photooxidation of chemisorbed polyhydroxyl alcohols and carbohydrates by TiO2 nanoparticles in an aqueous solution

Time-resolved transient absorption spectroscopy has been used to study nanosecond and sub-microsecond electron dynamics in aqueous anatase nanoparticles in the presence of hole scavengers: chemisorbed polyols and carbohydrates. These polyhydroxylated compounds are rapidly oxidized by the holes; 50-60% of these holes are scavenged within the duration of 355 nm excitation laser pulse. The scavenging efficiency rapidly increases with the number of anchoring hydroxyl groups and varies considerably as a function of the carbohydrate structure. A specific binding site for the polyols and carbohydrates is suggested that involves an octahedral Ti atom chelated by the poly-OH ligand. This mode of binding accounts for the depletion of undercoordinated Ti atoms observed in the XANES spectra of polyol coated nanoparticles. We suggest that these binding sites trap a substantial fraction of holes before the latter descend to surface traps and/or recombine with free electrons. The resulting oxygen hole center rapidly loses a CH proton to the environment, yielding a metastable C-centered radical.

physics.chem-ph↗