53,651 research outputs found
Electron transfer with core-level excitations at hybrid interfaces
No full textElectron core-level spectroscopies have emerged as effective tools to investigate several aspects of the hybrid interface between organic molecules and a substrate. In particular, resonant photoemission spectroscopy can measure interfacial electron transfer times down to the femtosecond timescale. Furthermore, the strong perturbation induced by the core hole opens up the several questions on how the properties of the interface are modified, calling for a theoretical description of the core-excited system.
We adopt a theoretical framework based on density-functional theory (DFT), where the excitation is introduced explicitly in the core-level occupation of an atom in a molecule, to investigate the electronic structure and electron transfer from/to organic molecules adsorbed on metal, semimetal, and semiconducting substrates.
The perturbing potential lowers the energy of the molecular orbitals. Focusing on the lowest-unoccupied (LUMO), a filling of the core-excited LUMO* by substrate electrons may occur within the core-hole lifetime, as found for molecules on metals where the adsorption angle is also shown to influence the electron transfer rate [1,2]. In the case of a semimetal graphene substrate, a spin-polarized LUMO* pinned at the Fermi level can be determined for physisorbed molecules. In that case electron transfer would be suppressed given the low density of states of unsupported graphene at that energy, but still possible for graphene supported on a metal [3]. For molecules adsorbed on a semiconductor, the LUMO* may form a bound exciton in the gap [4]. Here, we found especially interesting to consider the influence of thermal motion on the energy-level alignment and the absorption coefficient [5,6].
References
[1] D. Cvetko, G. Fratesi, G. Kladnik, A. Cossaro, G.P. Brivio, L. Venkataraman, and A. Morgante, submitted.
[2] A. Baby, G. Fratesi, S.R. Vaidya, L.L. Patera, C. Africh, L. Floreano, G.P. Brivio, J. Phys. Chem. C 119 (2015) 3624.
[3] A. Ravikumar, A. Baby, H. Lin, G.P. Brivio, and G. Fratesi, Scientific Reports 6 (2016) 24603.
[4] G. Fratesi, C. Motta, M. I. Trioni, G. P. Brivio, and D. Sánchez-Portal, J. Phys. Chem. C 118 (2014) 8775
[5] H. Lin, G. Fratesi, S. Selçuk, G.P. Brivio, and A. Selloni, J. Phys. Chem. C, 120 (2016) 3899.
[6] M. Muller, D. Sànchez-Portal, H. Lin, G. Fratesi, G.P. Brivio, and A. Selloni, in preparation
FIGURE 2. Aristolochia gurinderii K in Aristolochia gurinderii (Aristolochiaceae): a new species from Great Nicobar Island, India
No full textFIGURE 2. Aristolochia gurinderii K. Ravikumar, Umeshkumar Tiwari and N. Balachandran, sp. nov.: A. Leaf with fruit; B. Inflorescence; C. Flower patterns; D. Close up of Flower; E. Dry Fruits and F. Green Fruit (Type: FRLH).Published as part of Ravikumar, K., Tiwari, Umeshkumar & Balachandran, N., 2014, Aristolochia gurinderii (Aristolochiaceae): a new species from Great Nicobar Island, India, pp. 117-122 in Phytotaxa 172 (2) on page 120, DOI: 10.11646/phytotaxa.172.2.7, http://zenodo.org/record/514244
Tuning ultrafast electron injection dynamics at organic-graphene/metal interfaces
No full textThe properties of novel and prospective 2D materials are dramatically influenced by the interaction with a substrate. For example, the electronic hybridization of silicene states on Ag(111) or graphene ones on Ni(111) disrupts the Dirac fermions of the freestanding layers. This calls for efficient approaches to tune the interaction strength at the interface. Here we focus on the case of graphene functionalized by organic molecules and grown on Ni(111) and on the interfacial charge transfer dynamics. This is investigated by X-ray resonant photoemission spectroscopy, that is able to measure electron transfer rates occurring within few femtoseconds, and by a theoretical framework based on density-functional theory [1,2].
We use 4,4’-bipyridine as the prototypical molecule for these explorations as the energy level alignment of core-excited molecular orbitals allows ultrafast injection (τ=4fs) of electrons from the substrate to the molecule adsorbed on epitaxial graphene/Ni(111), which is characterized by a strong hybridization between C and metal states. We demonstrate that this interface can be decoupled by the addition of a second layer of graphene, where the one in contact with the metal acts as a buffer layer and the one in contact with the molecule is less hybridized with Ni underneath. As a result, the ultrafast injection of electrons from the substrate to the molecule is ∼4 times slower on weakly coupled bilayer graphene than on epitaxial graphene. Through our experiments and calculations, we can attribute this to a difference in the density of states close to the Fermi level between graphene and bilayer graphene. We therefore show how graphene coupling with the substrate influences charge transfer dynamics between organic molecules and graphene interfaces.
[1] G. Fratesi, C. Motta, M. I. Trioni, G. P. Brivio, and D. Sánchez-Portal, J. Phys. Chem. C 118, 8775 (2014)
[2] D. Cvetko, G. Fratesi, G. Kladnik, A. Cossaro, G.P. Brivio, L. Venkataraman, and A. Morgante, Phys. Chem. Chem. Phys. 18, 22140 (2016)
[3] A. Ravikumar, G. Kladnik, M. Müller, A. Cossaro, G. Bavdek, L. Patera, D. Sánchez-Portal, L. Venkataraman, A. Morgante, G. P. Brivio, D. Cvetko, and G. Fratesi, Nanoscale 10, 8014 (2018)
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Effect of Ru surface composition on the CO tolerance of Ru modified carbon supported Pt catalysts
No full textA series of ruthenium modified carbon supported catalysts have been prepared by surface organometallic chemistry (SOMC) with the following nominal Ru:Pt surface ratios, (1:4)RuPt/C, (1:2)RuPt/C, (3:4)RuPt/C and (1:1)RuPt/C. The catalysts were characterised using X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS), cyclic voltammetry (CV), and half-cell polarisation studies. The XRD measurements showed that a bulk PtRu alloy was not formed following SONIC modification. However, the EXAFS measurements indicated that a surface alloy is formed upon electrochemical reduction of the Ru modified catalysts. The CV studies show that the electrooxidation of CO on the Ru modified Pt/C catalysts occurs at lower potentials than on the unmodified Pt/C catalysts, but at higher potentials than on an alloyed PtRu/C with a bulk composition of 1:1 Pt:Ru. Half cell polarisation measurements in 100 ppm CO in H-2 show that the CO tolerance of the SONIC RuPt/C catalysts approached that of the conventional PtRu/C alloy catalyst. The results therefore indicate that a bulk alloy phase is not an essential factor in the improvement in CO tolerance of PtRu/C catalysts over that of Pt/C
Measurement of the D+/- production asymmetry in 7 TeV pp collisions
No full textThe asymmetry in the production cross-section \sigma of D+/- mesons, A_P = (\sigma(D+) - \sigma(D-))/(\sigma(D+) + \sigma(D-)), is measured in bins of pseudorapidity \eta and transverse momentum p_T within the acceptance of the LHCb detector. The result is obtained with a sample of D+ -> K_S pi+ decays corresponding to an integrated luminosity of 1.0 fb^-1, collected in pp collisions at a centre of mass energy of 7 TeV at the Large Hadron Collider. When integrated over the kinematic range 2.0 K_S pi+ decay is negligible. No significant dependence on \eta or p_T is observed
D* (D)over-bar* molecule interpretation of Z(c)(4025)
No full textWe have used QCD sum rules to study the newly observed charged state Z(c)(4025) as a hidden-charm D*(D) over bar* molecular state with the quantum numbers I-G(J(P)) =1(+)(1(+)). Using a D*(D) over bar* molecular interpolating current, we have calculated the two-point correlation function and the spectral density up to dimension eight at leading order in alpha(s). The extracted mass is m(X) = (4.04 +/- 0.24) GeV. This result is compatible with the observed mass of Z(c)(4025) within the errors, which implies a possible molecule interpretation of this new resonance. We also predict the mass of the corresponding hidden-bottom B*(B) over bar* molecular state: m(Zb) = (9.98 +/- 0.21) GeV.Physics, Particles & FieldsSCI(E)[email protected]; [email protected]; [email protected]; [email protected]
Prompt charm production in pp collisions at √<span style="text-decoration:overline">s</span>=7 TeV
No full textCharm production at the LHC in pp collisions at s√=7 TeV is studied with the LHCb detector. The decays D0→K−π+, D+→K−π+π+, D⁎+→D0(K−π+)π+, D+s→ϕ(K−K+)π+, Λ+c→pK−π+, and their charge conjugates are analysed in a data set corresponding to an integrated luminosity of 15 nb−1. Differential cross-sections dσ/dpT are measured for prompt production of the five charmed hadron species in bins of transverse momentum and rapidity in the region 0<pT<8 GeV/c and 2.0<y<4.5. Theoretical predictions are compared to the measured differential cross-sections. The integrated cross-sections of the charm hadrons are computed in the above pT-y range, and their ratios are reported. A combination of the five integrated cross-section measurements gives
σ(cc¯)pT<8 GeV/c,2.0<y<4.5=1419±12(stat)±116(syst)±65(frag) μb,
where the uncertainties are statistical, systematic, and due to the fragmentation functions
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