Excited state dynamics of liquid water: Insight from the dissociation reaction following two-photon excitation

We use transient absorption spectroscopy to monitor the ionization and dissociation products following two-photon excitation of pure liquid water. The two decay mechanisms occur with similar yield for an excitation energy of 9.3 eV, whereas the major channel at 8.3 eV is dissociation. The geminate recombination kinetics of the H and OH fragments, which can be followed in the transient absorption probed at 267 nm, provide a window on the dissociation dynamics at the lower excitation energy. Modeling the OH geminate recombination indicates that the dissociating H atoms have enough kinetic energy to escape the solvent cage and one or two additional solvent shells. The average initial separation of H and OH fragments is 0.7+-0.2 nm. Our observation suggests that the hydrogen bonding environment does not prevent direct dissociation of an O-H bond in the excited state. We discuss the implications of our measurement for the excited state dynamics of liquid water and explore the role of those dynamics in the ionization mechanism at low excitation energies

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.Comment: 34 pages, 12 figures; to be submitted to J Phys Chem

Dark matter search results from the PICO-60 CF3I 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 CF3I 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 C3F8 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.The PICO Collaboration would like to thank SNOLAB and its staff for providing an exceptional underground laboratory space and invaluable technical support. We acknowledge technical assistance from Fermilab's Computing, Particle Physics, and Accelerator Divisions and from A. Behnke at IUSB. We thank V. Gluscevic and S. McDermott for useful conversations and their assistance with the DMDD code package. This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of High Energy Physics under Award No. DE-SC-0012161. Fermi National Accelerator Laboratory is operated by Fermi Research Alliance, LLC under Contract No. De-AC02-07CH11359. Part of the research described in this paper was conducted under the Ultra Sensitive Nuclear Measurements Initiative at Pacific Northwest National Laboratory, a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy. We acknowledge the National Science Foundation for their support including Grants No. PHY-1242637, No. PHY-0919526, and No. PHY-1205987. We acknowledge the support of the National Sciences and Engineering Research Council of Canada (NSERC) and the Canada Foundation for Innovation (CFI). We thank the Kavli Institute for Cosmological Physics at the University of Chicago. We were also supported by the Spanish Ministerio de Economia y Competitividad, Consolider MultiDark CSD2009-00064 Grant. We thank the Department of Atomic Energy (DAE), Government of India, under the project CAPP-II at SINP, Kolkata. 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