J. Appl. Cryst.の発刊に際して

Most of the energy deposited in cells by ionizing radiation is channeled into the production of abundant free secondary electrons with ballistic energies between 1 and 20 electron volts. Here it is shown that reactions of such electrons, even at energies well below ionization thresholds, induce substantial yields of single- and double-strand breaks in DNA, which are caused by rapid decays of transient molecular resonances localized on the DNA's basic components. This finding presents a fundamental challenge to the traditional notion that genotoxic damage by secondary electrons can only occur at energies above the onset of ionization, or upon solvation when they become a slowly reacting chemical species.

http://science.sciencemag.org/content/sci/287/5458/1658.full.pdf

Resonant Formation of DNA Strand Breaks by Low-Energy (3 to 20 eV) Electrons

We point out a general framework that encompasses most cases in which quantum effects enable an increase in precision when estimating a parameter (quantum metrology) The typical quantum precision-enhancement is of the order of the square root of the number of times the system is sampled We prove that this is optimal and we point out the different strategies (classical and quantum) that permit to attain this bound

Quantum metrology

Noncovalent interactions: a challenge for experiment and theory

I. Introduction and Scope 231A. Definitions of Atomic Electron Affinities 233B. Definitions of Molecular Electron Affinities 233II. Experimental Photoelectron Electron Affinities 235A. Historical Background 235B. The Photoeffect 236C. Experimental Methods 237D. Time-of-Flight Negative Ion PhotoelectronSpectroscopy239E. Some Thermochemical Uses of ElectronAffinities241F. Layout of Table 10: ExperimentalPhotoelectron Electron Affinities242III. Theoretical Determination of Electron Affinities 242A. Historical Background 2421. Theoretical Predictions of Atomic ElectronAffinities2422. Theoretical Predictions of MolecularElectron Affinities243B. Present Status of Theoretical Electron AffinityPredictions243C. Basis Sets and Theoretical Electron Affinities 244D. Density Functional Theory (DFT) andElectron Affinities245E. Layout of Tables 8 and 9: Theoretical DFTElectron Affinities247F. Details of Density Functional MethodsEmployed in Tables 8 and 9247IV. Discussion and Observations 248A. Statistical Analysis of DFT Results ThroughComparisons to Experiment and OtherTheoretical Methods248B. Theoretical EAs for Species with UnknownExperimental EAs251C. On the Applicability of DFT to Anions and theFuture of DFT EA Predictions251D. Specific Theoretical Successes 251E. Interesting Problems 2521. C

/pdf/atomic-and-molecular-electron-affinities-photoelectron-3x4vklpj6q.pdf

Atomic and molecular electron affinities: photoelectron experiments and theoretical computations.

The anions of the nucleic acid bases, uracil and thymine, were studied by negative ion photoelectron spectroscopy. Both monomer anions exhibit spectroscopic signatures that are indicative of dipole bound excess electrons. The adiabatic electron affinities of these molecules were found to be 93±7 meV for uracil and 69±7 meV for thymine. No conventional (valence) anions of these molecules were observed.

https://pages.jh.edu/chem/bowen/Publication%20PDF/Dipole%20bound,%20nucleic%20acid%20base%20anions%20studied%20via%20negative%20ion.pdf

Dipole bound, nucleic acid base anions studied via negative ion photoelectron spectroscopy

Nucleic acid base anions play an important role in radiation-induced mutagenesis. Recently, it has been shown that isolated (gas-phase) nucleobases form an exotic form of negative ions, namely, dipole bound anions. These are species in which the excess electrons are bound by the dipole fields of the neutral molecules. In the condensed phase, on the other hand, nucleobase anions are known to be conventional (covalent) anions, implying the transformation from one form into the other due to environmental (solvation) effects. Here, in a series of negative ion photoelectron spectroscopic experiments on gas-phase, solvated uracil cluster anions, we report the observation of this transformation.

/pdf/the-dipole-bound-to-covalent-anion-transformation-in-uracil-3gugn6pc2i.pdf

The dipole bound-to-covalent anion transformation in uracil

~Received 28 December 1995; accepted 9 May 1996! Conventional ~valence! and dipole-bound anions of the nitromethane molecule are studied using negative ion photoelectron spectroscopy, Rydberg charge exchange and field detachment techniques. Reaction rates for charge exchange between Cs(ns,nd) and Xe( nf ) Rydberg atoms with CH 3 NO 2 exhibit a pronounced maximum at an effective quantum number of n*’1361 which is characteristic of the formation of dipole-bound anions @m~CH 3 NO 2 !53.46 D#. However, the breadth ~Dn’5, FWHM! of the n-dependence of the reaction rate is also interpreted to be indicative of direct attachment into a valence anion state via a ‘‘doorway’’ dipole anion state. Studies of the electric field detachment of CH 3NO2 formed through the Xe( nf ) reactions at various n values provide further evidence for the formation of both a dipole-bound anion as well as a contribution from the valence bound anion. Analysis of the field ionization data yields a dipole electron affinity of 1263 meV. Photodetachment of CH3NO2 and CD3NO2 formed via a supersonic expansion nozzle ion source produces a photoelectron spectrum with a long vibrational progression indicative of a conventional ~valence bound! anion with a substantial difference in the equilibrium structure of the anion and its corresponding neutral. Assignment of the origin ~v850, v950! transitions in the photoelectron spectra of CH3NO2 and CD3NO2 yields adiabatic electron affinities of 0.2660.08 and 0.2460.08 eV, respectively. © 1996 American Institute of Physics.@S0021-9606~96!02831-0#

/pdf/on-the-binding-of-electrons-to-nitromethane-dipole-and-n730lrewhd.pdf

On the binding of electrons to nitromethane: Dipole and valence bound anions

In situ Raman spectroscopic investigation of chromium surfaces under hydrothermal conditions

In situ Raman spectroscopy was employed to investigate iron corrosion in air saturated water at a pressure of 25.1 MPa and temperatures from 21 to 537°C. Upon heating, various combinations of Fe 3 O 4 . α-Fe 2 O 3 , γ-FeOOH, and γ-Fe 2 O 3 were observed depending on the location on or temperature of the iron coupon. In some cases, different species were observed at the same temperature at different locations on the surface. This was attributed to oxygen concentration gradients in the solution caused by recirculation zones in the cell. The surface of the corrosion coupon changed little after it was heated to 537°C. This was attributed to the formation of a relatively thick, protective oxide scale after exposure to supercritical water. The ex situ Raman spectra were very similar to the in situ spectra obtained during cooling but different from those obtained during heating. This indicates that the corrosion layer present during cooling is similar to that observed ex situ but different from that observed during heating. Ex situ characterization of the coupon identified a two layered structure: an inner corrosion layer consisting of Fe 3 O 4 and α-Fe 2 O 3 and an outer layer consisting of γ-Fe 2 O 3 and α-Fe 2 O 3 .

Jay H. Hendricks

Papers

Dipole bound, nucleic acid base anions studied via negative ion photoelectron spectroscopy

The dipole bound-to-covalent anion transformation in uracil

On the binding of electrons to nitromethane: Dipole and valence bound anions

In situ Raman spectroscopic investigation of chromium surfaces under hydrothermal conditions

In Situ Raman Spectroscopic Investigation of Aqueous Iron Corrosion at Elevated Temperatures and Pressures