Correlation between Accurate Electron Density and Linear Optical Properties in Amino Acid Derivatives: L-Histidinium Hydrogen Oxalate

The accurate electron density and linear optical properties of L-histidinium hydrogen oxalate are discussed. Two high-resolution single crystal X-ray diffraction experiments were performed and compared with density functional calculations in the solid state as well as in the gas phase. The crystal packing and the hydrogen bond network are accurately investigated using topological analysis based on quantum theory of atoms in molecules, Hirshfeld surface analysis, and electrostatic potential mapping. The refractive indices are computed from couple perturbed Kohn-Sham calculations and measured experimentally. Moreover, distributed atomic polarizabilities are used to analyze the origin of the linear susceptibility in the crystal, in order to separate molecular and intermolecular causes. The optical properties are also correlated with the electron density distribution. This compound also offers the possibility to test the electron density building block approach for material science and different refinement schemes for accurate positions and displacement parameters of hydrogen atoms, in the absence of neutron diffraction data.

Calculation of crystal optical properties from molecular electron density

We have recently developed a method to obtain distributed atomic polarizabilities adopting a partitioning of the molecular electron density (for example, the Quantum Theory of Atoms in Molecules, [1]), calculated with or without an applied electric field. The procedure [2] allows to obtained atomic polarizability tensors, which are perfectly exportable, because quite representative of an atom in a given functional group. Among the many applications of this idea, the calculation of crystal susceptibility is easily available, either from a rough estimation (the polarizability of the isolated molecule is used) or from a more precise estimation (the polarizability of a molecule embedded in a cluster representing the first coordination sphere is used). Lorentz factor is applied to include the long range effect of packing, which is enhancing the molecular polarizability. Simple properties like linear refractive index or the gyration tensor can be calculated at relatively low costs and with good precision. This approach is particularly useful within the field of crystal engineering of organic/organometallic materials, because it would allow a relatively easy prediction of a property as a function of the packing, thus allowing "reverse crystal engineering". Examples of some amino acid crystals and salts of amino acids [3] will be illustrated, together with other crystallographic or non-crystallographic applications. For example, the induction and dispersion energies of intermolecular interactions could be calculated with superior precision (allowing anisotropic van der Waals interactions). This could allow revision of some commonly misunderstood intermolecular interactions, like the halogen bonding (see for example the recent remarks by Stone or Gilli [4]). Moreover, the chemical reactivity of coordination complexes could be reinvestigated, by coupling the conventional analysis of the electrostatic potential (useful only in the circumstances of hard nucleophilic/electrophilic interaction) with the distributed atomic polarizability. The enhanced reactivity of coordinated organic ligands would be better appreciated. [1] R. F. W. Bader, Atoms in Molecules: A Quantum Theory. Oxford Univ. Press, 1990. [2] A. Krawczuk-Pantula, D. Pérez, K. Stadnicka, P. Macchi, Trans. Amer. Cryst. Ass. 2011, 1-25 [3] A. S. Chimpri1, M. Gryl, L. H.R. Dos Santos1, A. Krawczuk, P. Macchi Crystal Growth & Design, in the press. [4] a) A. J. Stone, J. Am. Chem. Soc. 2013, 135, 7005−7009; b) V. Bertolasi, P. Gilli, G. Gilli Crystal Growth & Design, 2013, 12, 4758-4770.

Measurement of the Inclusive NuMu Charged Current Cross Section on Carbon in the Near Detector of the T2K

T2K has performed the first measurement of nu(mu) inclusive charged current interactions on carbon at neutrino energies of similar to 1 GeV where the measurement is reported as a flux-averaged double differential cross section in muon momentum and angle. The flux is predicted by the beam Monte Carlo and external data, including the results from the NA61/SHINE experiment. The data used for this measurement were taken in 2010 and 2011, with a total of 10.8 x 10(19) protons-on-target. The analysis is performed on 4485 inclusive charged current interaction candidates selected in the most upstream fine-grained scintillator detector of the near detector. The flux-averaged total cross section is (phi) = (6.91 +/- 0.13(stat) +/- 0.84(syst)) x 10(-39) cm(2)/nucleon for a mean neutrino energy of 0.85 GeV.

Improved predictions for μ\to e conversion in nuclei and Higgs-induced lepton flavor violation

Compared to μ→eγ and μ→eee, the process μ→e conversion in nuclei receives enhanced contributions from Higgs-induced lepton flavor violation. Upcoming μ→e conversion experiments with drastically increased sensitivity will be able to put extremely stringent bounds on Higgs-mediated μ→e transitions. We point out that the theoretical uncertainties associated with these Higgs effects, encoded in the couplings of quark scalar operators to the nucleon, can be accurately assessed using our recently developed approach based on SU(2) chiral perturbation theory that cleanly separates two- and three-flavor observables. We emphasize that with input from lattice QCD for the coupling to strangeness fNs, hadronic uncertainties are appreciably reduced compared to the traditional approach where fNs is determined from the pion-nucleon σ term by means of an SU(3) relation. We illustrate this point by considering Higgs-mediated lepton flavor violation in the standard model supplemented with higher-dimensional operators, the two-Higgs-doublet model with generic Yukawa couplings, and the minimal supersymmetric standard model. Furthermore, we compare bounds from present and future μ→e conversion and μ→eγ experiments.

Measurement of long-range pseudorapidity correlations and azimuthal harmonics in √s_NN=5.02 TeV proton-lead collisions with the ATLAS detector

Measurements of two-particle correlation functions and the first five azimuthal harmonics, v 1 to v 5 , are presented, using 28 nb −1 of p+Pb collisions at a nucleon-nucleon center-of-mass energy of √s NN=5.02 TeV measured with the ATLAS detector at the LHC. Significant long-range “ridgelike” correlations are observed for pairs with small relative azimuthal angle (|Δϕ|<π/3 ) and back-to-back pairs (|Δϕ|>2π/3 ) over the transverse momentum range 0.4

4 GeV. The v 2 (p T ) , v 3 (p T ) , and v 4 (p T ) are compared to the v n coefficients in Pb+Pb collisions at √s NN=2.76 TeV with similar event multiplicities. Reasonable agreement is observed after accounting for the difference in the average p T of particles produced in the two collision systems.

Search for new particles in events with one lepton and missing transverse momentum in pp collisions at √s = 8 TeV with the ATLAS detector

This paper presents a search for new particles in events with one lepton (electron or muon) and missing transverse momentum using 20.3 fb−1 of proton-proton collision data at TeX = 8 TeV recorded by the ATLAS experiment at the Large Hadron Collider. No significant excess beyond Standard Model expectations is observed. A W ′ with Sequential Standard Model couplings is excluded at the 95% confidence level for masses up to 3.24 TeV. Excited chiral bosons (W *) with equivalent coupling strengths are excluded for masses up to 3.21 TeV. In the framework of an effective field theory limits are also set on the dark matter-nucleon scattering cross-section as well as the mass scale M * of the unknown mediating interaction for dark matter pair production in association with a leptonically decaying W.

Search for Invisible Decays of a Higgs Boson Produced in Association with a Z Boson in ATLAS

A search for evidence of invisible-particle decay modes of a Higgs boson produced in association with a Z boson at the Large Hadron Collider is presented. No deviation from the standard model expectation is observed in 4.5 fb−1 (20.3 fb−1) of 7 (8) TeV pp collision data collected by the ATLAS experiment. Assuming the standard model rate for ZH production, an upper limit of 75%, at the 95% confidence level is set on the branching ratio to invisible-particle decay modes of the Higgs boson at a mass of 125.5 GeV. The limit on the branching ratio is also interpreted in terms of an upper limit on the allowed dark matter-nucleon scattering cross section within a Higgs-portal dark matter scenario. Within the constraints of such a scenario, the results presented in this Letter provide the strongest available limits for low-mass dark matter candidates. Limits are also set on an additional neutral Higgs boson, in the mass range 110 < mH < 400 GeV, produced in association with a Z boson and decaying to invisible particles.

Neutrino physics with multi-ton scale liquid xenon detectors

We study the sensitivity of large-scale xenon detectors to low-energy solar neutrinos, to coherent neutrino-nucleus scattering and to neutrinoless double beta decay. As a concrete example, we consider the xenon part of the proposed DARWIN (Dark Matter WIMP Search with Noble Liquids) experiment. We perform detailed Monte Carlo simulations of the expected backgrounds, considering realistic energy resolutions and thresholds in the detector. In a low-energy window of 2–30 keV, where the sensitivity to solar pp and 7Be-neutrinos is highest, an integrated pp-neutrino rate of 5900 events can be reached in a fiducial mass of 14 tons of natural xenon, after 5 years of data. The pp-neutrino flux could thus be measured with a statistical uncertainty around 1%, reaching the precision of solar model predictions. These low-energy solar neutrinos will be the limiting background to the dark matter search channel for WIMP-nucleon cross sections below ~2X 10-48 cm2 and WIMP masses around 50 GeV c 2, for an assumed 99.5% rejection of electronic recoils due to elastic neutrino-electron scatters. Nuclear recoils from coherent scattering of solar neutrinos will limit the sensitivity to WIMP masses below ~6 GeV c-2 to cross sections above ~4X10-45cm2. DARWIN could reach a competitive half-life sensitivity of 5.6X1026 y to the neutrinoless double beta decay of 136Xe after 5 years of data, using 6 tons of natural xenon in the central detector region.

Measurement of the TeV atmospheric muon charge ratio with the complete OPERA data set

The OPERA detector, designed to search for νμ → ντ oscillations in the CNGS beam, is located in the underground Gran Sasso laboratory, a privileged location to study TeV-scale cosmic rays. For the analysis here presented, the detector was used to measure the atmospheric muon charge ratio in the TeV region. OPERA collected chargeseparated cosmic ray data between 2008 and 2012. More than 3 million atmospheric muon events were detected and reconstructed, among which about 110000 multiple muon bundles. The charge ratio Rμ ≡ Nμ+/Nμ− was measured separately for single and for multiple muon events. The analysis exploited the inversion of the magnet polarity which was performed on purpose during the 2012 Run. The combination of the two data sets with opposite magnet polarities allowedminimizing systematic uncertainties and reaching an accurate determination of the muon charge ratio. Data were fitted to obtain relevant parameters on the composition of primary cosmic rays and the associated kaon production in the forward fragmentation region. In the surface energy range 1–20 TeV investigated by OPERA, Rμ is well described by a parametric model including only pion and kaon contributions to themuon flux, showing no significant contribution of the prompt component. The energy independence supports the validity of Feynman scaling in the fragmentation region up to 200 TeV/nucleon primary energy.

Measurement of the Inclusive Electron Neutrino Charged Current Cross Section on Carbon with the T2K Near Detector

The T2K off-axis near detector ND280 is used to make the first differential cross-section measurements of electron neutrino charged current interactions at energies ∼1  GeV as a function of electron momentum, electron scattering angle, and four-momentum transfer of the interaction. The total flux-averaged νe charged current cross section on carbon is measured to be ⟨σ⟩ϕ=1.11±0.10(stat)±0.18(syst)×10−38  cm2/nucleon. The differential and total cross-section measurements agree with the predictions of two leading neutrino interaction generators, NEUT and GENIE. The NEUT prediction is 1.23×10−38  cm2/nucleon and the GENIE prediction is 1.08×10−38  cm2/nucleon. The total νe charged current cross-section result is also in agreement with data from the Gargamelle experiment.

Detection of back-to-back proton pairs in charged-current neutrino interactions with the ArgoNeuT detector in the NuMI low energy beam line

Short range nucleon-nucleon correlations in nuclei (NN SRC) carry important information on nuclear structure and dynamics. NN SRC have been extensively probed through two-nucleon knock- out reactions in both pion and electron scattering experiments. We report here on the detection of two-nucleon knock-out events from neutrino interactions and discuss their topological features as possibly involving NN SRC content in the target argon nuclei. The ArgoNeuT detector in the Main Injector neutrino beam at Fermilab has recorded a sample of 30 fully reconstructed charged current events where the leading muon is accompanied by a pair of protons at the interaction vertex, 19 of which have both protons above the Fermi momentum of the Ar nucleus. Out of these 19 events, four are found with the two protons in a strictly back-to-back high momenta configuration directly observed in the final state and can be associated to nucleon Resonance pionless mechanisms involving a pre-existing short range correlated np pair in the nucleus. Another fraction (four events) of the remaining 15 events have a reconstructed back-to-back configuration of a np pair in the initial state, a signature compatible with one-body Quasi Elastic interaction on a neutron in a SRC pair. The detection of these two subsamples of the collected (mu- + 2p) events suggests that mechanisms directly involving nucleon-nucleon SRC pairs in the nucleus are active and can be efficiently explored in neutrino-argon interactions with the LAr TPC technology.

Light stops, blind spots, and isospin violation in the MSSM

In the framework of the MSSM, we examine several simplified models where only a few superpartners are light. This allows us to study WIMP-nucleus scattering in terms of a handful of MSSM parameters and thereby scrutinize their impact on dark matter direct-detection experiments. Focusing on spin-independent WIMP-nucleon scattering, we derive simplified, analytic expressions for the Wilson coefficients associated with Higgs and squark exchange. We utilize these results to study the complementarity of constraints due to direct-detection, flavor, and collider experiments. We also identify parameter configurations that produce (almost) vanishing cross sections. In the proximity of these so-called blind spots, we find that the amount of isospin violation may be much larger than typically expected in the MSSM. This feature is a generic property of parameter regions where cross sections are suppressed, and highlights the importance of a careful analysis of the nucleon matrix elements and the associated hadronic uncertainties. This becomes especially relevant once the increased sensitivity of future direct-detection experiments corners the MSSM into these regions of parameter space.

Materials properties from electron density distributions: Molecular magnetism and linear optical properties

The general goal of this thesis is correlating observable properties of organic and metal-organic materials with their ground-state electron density distribution. In a long-term view, we expect to develop empirical or semi-empirical approaches to predict materials properties from the electron density of their building blocks, thus allowing to rationally engineering molecular materials from their constituent subunits, such as their functional groups. In particular, we have focused on linear optical properties of naturally occurring amino acids and their organic and metal-organic derivatives, and on magnetic properties of metal-organic frameworks. For analysing the optical properties and the magnetic behaviour of the molecular or sub-molecular building blocks in materials, we mostly used the more traditional QTAIM partitioning scheme of the molecular or crystalline electron densities, however, we have also investigated a new approach, namely, X-ray Constrained Extremely Localized Molecular Orbitals (XC-ELMO), that can be used in future to extracted the electron densities of crystal subunits. With the purpose of rationally engineering linear optical materials, we have calculated atomic and functional group polarizabilities of amino acid molecules, their hydrogen-bonded aggregates and their metal-organic frameworks. This has enabled the identification of the most efficient functional groups, able to build-up larger electric susceptibilities in crystals, as well as the quantification of the role played by intermolecular interactions and coordinative bonds on modifying the polarizability of the isolated building blocks. Furthermore, we analysed the dependence of the polarizabilities on the one-electron basis set and the many-electron Hamiltonian. This is useful for selecting the most efficient level of theory to estimate susceptibilities of molecular-based materials. With the purpose of rationally design molecular magnetic materials, we have investigated the electron density distributions and the magnetism of two copper(II) pyrazine nitrate metal-organic polymers. High-resolution X-ray diffraction and DFT calculations were used to characterize the magnetic exchange pathways and to establish relationships between the electron densities and the exchange-coupling constants. Moreover, molecular orbital and spin-density analyses were employed to understand the role of different magnetic exchange mechanisms in determining the bulk magnetic behaviour of these materials. As anticipated, we have finally investigated a modified version of the X-ray constrained wavefunction technique, XC-ELMOs, that is not only a useful tool for determination and analysis of experimental electron densities, but also enables one to derive transferable molecular orbitals strictly localized on atoms, bonds or functional groups. In future, we expect to use XC-ELMOs to predict materials properties of large systems, currently challenging to calculate from first-principles, such as macromolecules or polymers. Here, we point out advantages, needs and pitfalls of the technique. This work fulfils, at least partially, the prerequisites to understand materials properties of organic and metal-organic materials from the perspective of the electron density distribution of their building blocks. Empirical or semi-empirical evaluation of optical or magnetic properties from a preconceived assembling of building blocks could be extremely important for rationally design new materials, a field where accurate but expensive first-principles calculations are generally not used. This research could impact the community in the fields of crystal engineering, supramolecular chemistry and, of course, electron density analysis.

The Role of Hydrogen Bond in Designing Molecular Optical Materials

In this perspective article, we revise some of the empirical and semi-empirical strategies for predicting how hydrogen bonding affects molecular and atomic polarizabilities in aggregates. We use p-nitroaniline and hydrated oxalic acid as working examples to illustrate the enhancement of donor and acceptor functional-group polarizabilities and their anisotropy. This is significant for the evaluation of electrical susceptibilities in crystals; and the properties derived from them like the refractive indices.

Dark matter sensitivity of multi-ton liquid xenon detectors

We study the sensitivity of multi ton-scale time projection chambers using a liquid xenon target, e.g., the proposed DARWIN instrument, to spin-independent and spin-dependent WIMP-nucleon scattering interactions. Taking into account realistic backgrounds from the detector itself as well as from neutrinos, we examine the impact of exposure, energy threshold, background rejection efficiency and energy resolution on the dark matter sensitivity. With an exposure of 200 t x y and assuming detector parameters which have been already demonstrated experimentally, spin-independent cross sections as low as 2.5×10−49 cm2 can be probed for WIMP masses around 40 GeV/c2. Additional improvements in terms of background rejection and exposure will further increase the sensitivity, while the ultimate WIMP science reach will be limited by neutrinos scattering coherently off the xenon nuclei.