Higher-order perturbative relativistic corrections to energies and properties

Relativistic effects need to be considered in quantum-chemical calculations on systems including heavy elements or when aiming at high accuracy for molecules containing only lighter elements. In the latter case, consideration of relativistic effects via perturbation theory is an attractive option. Among the available techniques, Direct Perturbation Theory (DPT) in its lowest order (DPT2) has become a standard tool for the calculation of relativistic corrections to energies and properties.In this work, the DPT treatment is extended to the next order (DPT4). It is demonstrated that the DPT4 correction can be obtained as a second derivative of the energy with respect to the relativistic perturbation parameter. Accordingly, differentiation of a suitable Lagrangian, thereby taking into account all constraints on the wave function, provides analytic expressions for the fourth-order energy corrections. The latter have been implemented at the Hartree-Fock level and within second-order Møller-Plesset perturbaton theory using standard analytic second-derivative techniques into the CFOUR program package. For closed-shell systems, the DPT4 corrections consist of higher-order scalar-relativistic effects as well as spin-orbit corrections with the latter appearing here for the first time in the DPT series.Relativistic corrections are reported for energies as well as for first-order electrical properties and compared to results from rigorous four-component benchmark calculations in order to judge the accuracy and convergence of the DPT expansion for both the scalar-relativistic as well as the spin-orbit contributions. Additionally, the importance of relativistic effects to the bromine and iodine quadrupole-coupling tensors is investigated in a joint experimental and theoretical study concerning the rotational spectra of CH2BrF, CHBrF2, and CH2FI.

Highly accurate quantum chemistry : spin-orbit splittings via multireference coupled-cluster methods and applications in heavy-atom main-group chemistry

Diese Dissertation demonstriert und verbessert die Vorhersagekraft der Coupled-Cluster-Theorie im Hinblick auf die hochgenaue Berechnung von Moleküleigenschaften. Die Demonstration erfolgt mittels Extrapolations- und Additivitätstechniken in der Single-Referenz-Coupled-Cluster-Theorie, mit deren Hilfe die Existenz und Struktur von bisher unbekannten Molekülen mit schweren Hauptgruppenelementen vorhergesagt wird. Vor allem am Beispiel von cyclischem SiS_2, einem dreiatomigen Molekül mit 16 Valenzelektronen, wird deutlich, dass die Vorhersagekraft der Theorie sich heutzutage auf Augenhöhe mit dem Experiment befindet: Theoretische Überlegungen initiierten eine experimentelle Suche nach diesem Molekül, was schließlich zu dessen Detektion und Charakterisierung mittels Rotationsspektroskopie führte. Die Vorhersagekraft der Coupled-Cluster-Theorie wird verbessert, indem eine Multireferenz-Coupled-Cluster-Methode für die Berechnung von Spin-Bahn-Aufspaltungen erster Ordnung in 2^Pi-Zuständen entwickelt wird. Der Fokus hierbei liegt auf Mukherjee's Variante der Multireferenz-Coupled-Cluster-Theorie, aber prinzipiell ist das vorgeschlagene Berechnungsschema auf alle Varianten anwendbar. Die erwünschte Genauigkeit beträgt 10 cm^-1. Sie wird mit der neuen Methode erreicht, wenn Ein- und Zweielektroneneffekte und bei schweren Elementen auch skalarrelativistische Effekte berücksichtigt werden. Die Methode eignet sich daher in Kombination mit Coupled-Cluster-basierten Extrapolations-und Additivitätsschemata dafür, hochgenaue thermochemische Daten zu berechnen.

Heavy metal cations permeate the TRPV6 epithelial cation channel

TRPV6 belongs to the vanilloid family of the transient receptor potential channel (TRP) superfamily. This calcium-selective channel is highly expressed in the duodenum and the placenta, being responsible for calcium absorption in the body and fetus. Previous observations have suggested that TRPV6 is not only permeable to calcium but also to other divalent cations in epithelial tissues. In this study, we tested whether TRPV6 is indeed also permeable to cations such as zinc and cadmium. We found that the basal intracellular calcium concentration was higher in HEK293 cells transfected with hTRPV6 than in non-transfected cells, and that this difference almost disappeared in nominally calcium-free solution. Live cell imaging experiments with Fura-2 and NewPort Green DCF showed that overexpression of human TRPV6 increased the permeability for Ca(2+), Ba(2+), Sr(2+), Mn(2+), Zn(2+), Cd(2+), and interestingly also for La(3+) and Gd(3+). These results were confirmed using the patch clamp technique. (45)Ca uptake experiments showed that cadmium, lanthanum and gadolinium were also highly efficient inhibitors of TRPV6-mediated calcium influx at higher micromolar concentrations. Our results suggest that TRPV6 is not only involved in calcium transport but also in the transport of other divalent cations, including heavy metal ions, which may have toxicological implications.

Sensitivity of charge transfer reactions to hydrocarbon ion structures

Charge transfer reactivities of hydrocarbon ions have been measured with time-of-flight techniques, and results correlated with theoretical structures computed by self-consistent field molecular orbital methods. Recombination energies, ion structures, heats of formation, reaction energetics and relative charge transfer cross-sections are presented for molecular and fragment ions produced by electron bombardment ionization of CH4, C2H4, C2H6, C3H8 and C4H10 molecules. Even-electron bridged cations have low ion recombination energies and relatively low charge transfer cross-sections as compared with odd-electron hydrocarbon cations.

Competition between single and double electron transfer in collisions of doubly charged molecular pyrrole ions with neutral pyrrole molecules

Cross-sections have been determined for one- and two-electron transfer channels in the collisions of keV gas-phase doubly charged pyrrole ions with pyrrole molecules. Measured single and double electron transfer total cross-sections approximate 45 Å2 and 15 Å2, respectively. A combination of symmetric resonance charge exchange and multistate curve-crossing models has been invoked to describe these reactions.

Thermal right-handed neutrino self-energy in the non-relativistic regime

Recently the issue of radiative corrections to leptogenesis has been raised. Considering the "strong washout" regime, in which OPE-techniques permit to streamline the setup, we report the thermal self-energy matrix of heavy right-handed neutrinos at NLO (resummed 2-loop level) in Standard Model couplings. The renormalized expression describes flavour transitions and "inclusive" decays of chemically decoupled right-handed neutrinos. Although CP-violation is not addressed, the result may find use in existing leptogenesis frameworks.

DESIGN AND DEVELOPMENT OF BODIPY-BASED FLUORESCENT PROBES FOR SENSING AND IMAGING OF CYANIDE, Zn (II) IONS, LYSOSOMAL pH AND CANCER CELLS

BODIPY (4,4-Difluoro-3a,4a-diaza-s-indacene) dyes have gained lots of attention in application of fluorescence sensing and imaging in recent years because they possess many distinctive and desirable properties such as high extinction coefficient, narrow absorption and emission bands, high quantum yield and low photobleaching effect. However, most of BODIPY-based fluorescent probes have very poor solubilities in aqueous solution, emit less than 650 nm fluorescence that can cause cell and tissue photodamages compared with bio-desirable near infrared (650-900 nm) light. These undesirable properties extremely limit the applications of BODIPY-based fluorescent probes in sensing and imaging applications. In order to overcome these drawbacks, we have developed a very effective strategy to prepare a series of neutral highly water- soluble BODIPY dyes by enhancing the water solubilities of BODIPY dyes via incorporation of tri(ethylene glycol)methyl ether (TEG) and branched oligo(ethylene glycol)methyl ether (BEG) residues onto BODIPY dyes at 1,7-, 2,6-, 3,5-, 4- and meso- positions. We also have effectively tuned absorptions and emissions of BOIDPY dyes to red, deep red and near infrared regions via significant extension of π-conjugation of BODIPY dyes by condensation reactions of aromatic aldehydes with 2,6-diformyl BODIPY dyes at 1,3,5,7-positions. Based on the foundation that we built for enhancing water solubility and tuning wavelength, we have designed and developed a series of water-soluble, BODIPY-based fluorescent probes for sensitive and selective sensing and imaging of cyanide, Zn (II) ions, lysosomal pH and cancer cells. We have developed three BODIPY-based fluorescent probes for sensing of cyanide ions by incorporating indolium moieties onto the 6-position of TEG- or BEG-modified BOIDPY dyes. Two of them are highly water-soluble. These fluorescent probes showed selective and fast ratiometric fluorescent responses to cyanide ions with a dramatic fluorescence color change from red to green accompanying a significant increase in fluorescent intensity. The detection limit was measured as 0.5 mM of cyanide ions. We also have prepared three highly water-soluble fluorescent probes for sensing of Zn (II) ions by introducing dipicoylamine (DPA, Zn ion chelator) onto 2- and/or 6-positions of BEG-modified BODIPY dyes. These probes showed selective and sensitive responses to Zn (II) ion in the range from 0.5 mM to 24 mM in aqueous solution at pH 7.0. Particularly, one of the probes displayed ratiometric responses to Zn (II) ions with fluorescence quenching at 661 nm and fluorescence enhancement at 521 nm. This probe has been successfully applied to the detection of intracellular Zn (II) ions inside the living cells. Then, we have further developed three acidotropic, near infrared emissive BODIPY- based fluorescent probes for detection of lysosomal pH by incorporating piperazine moiety at 3,5-positions of TEG- or BEG-modified BODIPY dyes as parts of conjugation. The probes have low auto-fluorescence at physiological neutral condition while their fluorescence intensities will significant increase at 715 nm when pH shift to acidic condition. These three probes have been successfully applied to the in vitro imaging of lysosomes inside two types of living cells. At the end, we have synthesized one water- soluble, near infrared emissive cancer cell targetable BODIPY-based fluorescent polymer bearing cancer homing peptide (cRGD) residues for cancer cell imaging applications. This polymer exhibited excellent water-solubility, near infrared emission (712 nm), good biocompatibility. It also showed low nonspecific interactions to normal endothelial cells and can effectively detect breast tumor cells.

Sommerfeld effect in heavy quark chemical equilibration

The chemical equilibration of heavy quarks in a quark-gluon plasma proceeds via annihilation or pair creation. For temperatures T much below the heavy quark mass M, when kinetically equilibrated heavy quarks move very slowly, the annihilation in the colour singlet channel is enhanced because the quark and antiquark attract each other which increases their probability to meet, whereas the octet contribution is suppressed. This is the so-called Sommerfeld effect. It has not been taken into account in previous calculations of the chemical equilibration rate, which are therefore incomplete for T ≲ α2sM . We compute the leading-order equilibration rate in this regime; there is a large enhancement in the singlet channel, but the rate is dominated by the octet channel, and therefore the total effect is small. In the course of the computation we demonstrate how operators that represent the annihilation of heavy quarks in non-relativistic QCD can be incorporated into the imaginary-time formalism.

Study of Heavy-ion Induced Fission for Heavy Element Synthesis

Fission fragment mass distributions were measured in heavy-ion induced fission of 238U. The mass distributions changed drastically with incident energy. The results are explained by a change of the ratio between fusion and quasifission with nuclear orientation. A calculation based on a fluctuation dissipation model reproduced the mass distributions and their incident energy dependence. Fusion probability was determined in the analysis. Evaporation residue cross sections were calculated with a statistical model for the reactions of 30Si+238U and 34S+238U using the obtained fusion probability in the entrance channel. The results agree with the measured cross sections of 263,264Sg and 267,268Hs, produced by 30Si+238U and 34S+238U, respectively. It is also suggested that sub-barrier energies can be used for heavy element synthesis.

Analysis and optimization of propagation losses in LiNbO3 optical waveguides produced by swift heavy-ion irradiation

The propagation losses (PL) of lithium niobate optical planar waveguides fabricated by swift heavy-ion irradiation (SHI), an alternative to conventional ion implantation, have been investigated and optimized. For waveguide fabrication, congruently melting LiNbO3 substrates were irradiated with F ions at 20 MeV or 30 MeV and fluences in the range 1013–1014 cm−2. The influence of the temperature and time of post-irradiation annealing treatments has been systematically studied. Optimum propagation losses lower than 0.5 dB/cm have been obtained for both TE and TM modes, after a two-stage annealing treatment at 350 and 375∘C. Possible loss mechanisms are discussed.

Relativistic current collection by a cylindrical Langmuir probe

The current I to a cylindrical Langmuir probe with a bias Φp satisfying β≡eΦp/mec2∼O(1) is discussed. The probe is considered at rest in an unmagnetized plasma composed of electrons and ions with temperatureskTe∼kTi≪mec2. For small enough radius, the probe collects the relativistic orbital-motion-limited (OML) current I OML , which is shown to be larger than the non-relativistic result; the OML current is proportional to β1/2 and β3/2 in the limits β≪1 and β≫1, respectively. Unlike the non-relativistic case, the electron density can exceed the unperturbed density value. An asymptotic theory allowed to compute the maximum radius of the probe to collect OML current, the sheath radius for probe radius well below maximum and how the ratio I/I OML drops below unity when the maximum radius is exceeded. A numerical algorithm that solves the Vlasov-Poisson system was implemented and density and potential profiles presented. The results and their implications in a possible mission to Jupiter with electrodynamic bare tethers are discussed density value. An asymptotic theory allowed to compute the maximum radius of the probe to collect OML current, the sheath radius for probe radius well below maximum and how the ratio I/IOML drops below unity when the maximum radius is exceeded. A numerical algorithm that solves the Vlasov-Poisson system was implemented and density and potential profiles presented. The results and their implications in a possible mission to Jupiter with electrodynamic bare tethers are discussed.

Swift heavy ion damage to sodium chloride: synergy between excitation and thermal spikes

Systematic data on the effect of irradiation with swift ions (Zn at 735 MeV and Xe at 929 MeV) on NaCl single crystals have been analysed in terms of a synergetic two-spike approach (thermal and excitation spikes). The coupling of the two spikes, simultaneously generated by the irradiation, contributes to the operation of a non-radiative exciton decay model as proposed for purely ionization damage. Using this scheme, we have accounted for the π-emission yield of self-trapped excitons and its temperature dependence under ion-beam irradiation. Moreover, the initial production rates of F-centre growth have also been reasonably simulated for irradiation at low temperatures ( < 100 K), where colour centre annealing and aggregation can be neglected.

Single - and double energy swift and slow heavy ion irradiated optical waveguides in Er: Tungstene-Tellurite glass and BGO for telecom applications

The fabrication of broadband amplifiers in wavelength division multiplexing (WDM) around 1.55 m, as they exhibit large stimulated cross sections and broad emission bandwidth. Bi4Ge3O12 (eultine type BGO) - well known scintillator material, also a rare-earth host material, photorefractive waveguides produced in it only using light ions in the past. Recently: MeV N+ ions and swift O5+ and C5+ ions, too*. Bi12GeO20 (sillenite type BGO) - high photoconductivity and photorefractive sensitivity in the visible and NIR good candidate for real-time holography and optical phase conjugation, photorefractive waveguides produced in it only using light ions. No previous attempts of ion beam fabrication of waveguides in it.

Ion-beam damage induced in SiO2: Excitonic mechanisms under heavy electronic excitation

The Centro de Micro-Análisis de Materiales (CMAM) in the Universidad Autónoma de Madrid is carrying out an extensive research program on the processes induced by high energy heavy mass ions (SHI) on dielectric materials and their photonic applications [1?21]. A significant part of this activity constitutes a relevant contribution to the scientific program associated to the TECHNOFUSION project. It is performed in collaboration with the Instituto de Fusion Nuclear at the UPM, the CIEMAT, the Departamento de Física de Materiales at UAM and several other national institutions (INTA) and international laboratories (GANIL, France), Legnaro Italy, Grenoble?. The program has led to a large number of publications in reputed international journals.

Relativistic screened hydrogenic radial integrals

The computation of dipole matrix elements plays an important role in the study of absorption or emission of radiation by atoms in several fields such as astrophysics or inertial confinement fusion. In this work we obtain closed formulas for the dipole matrix elements of multielectron ions suitable for using in the framework of a Relativistic Screened Hydrogenic Model.