Femtosecond vibrational dynamics of self-trapping in a quasi-one-dimensional system

We have directly time resolved the lattice motions associated with the formation of the self-trapped exciton in the quasi-one-dimensional system [Pt(en)(2)] [Pt(en)2Br2];(PF6)(4) ( en = ethylene-diamine, C2H8N2), using femtosecond impulsive excitation techniques. A strongly damped, low-frequency wave packet modulation at approximately 110 cm(-1) accompanies the formation of the self-trapped exciton on a approximately 200 fs time scale following excitation of the intervalence charge-transfer transition. Coherent oscillations at the ground state vibrational frequency and its harmonics are also detected.     

Wave packet dynamics in a quasi-one-dimensional metal-halogen complex studied by ultrafast time-resolved spectroscopy

An ultrafast optical response is studied in a quasi-one-dimensional halogen-bridged mixed-valence metal complex [Pt(en)(2)] [Pt(en)2I2] (ClO4)(4) with ultrafast time resolution. Wave packet motions both in the ground and self-trapped exciton (STE) states are observed as oscillatory modulations in the time-resolved reflectivity. The wave packet motion on the STE potential surface begins after about 50 fs with respect to the photoexcitation. This delay is attributed to the lattice relaxation from the free exciton state to the STE state.     

Novel optical and magnetic bistability and photoinduced transition in a one-dimensional halogen-bridged binuclear pt complex

In iodine-bridged binuclear Pt compounds, R(4)[Pt(2)(pop)(4)I]nH(2)O and R(')(2)[Pt(2)(pop)(4)I]nH(2)O (pop=P(2)O5H2-2), electronic structures on the PtPtI chains have been controlled between a diamagnetic charge-density-wave (CDW) state and a paramagnetic charge-polarization (CP) state by modification of the counterions (R, R') located between chains. In the R=(C2H5)2NH+2 compound, a pressure-induced CP to CDW transition with a drastic color change is identified. This transition is accompanied by a large hysteresis loop within which photoinduced transition between CDW and CP can be driven by selecting the excitation photon energy.     

The Electroabsorption in Quasi-One-Dimensional Halogen-Bridged Mixed-Valence Platinum Complexes

The electroa bsorp tion spectra of the halogen- bridged mixed-valence Pt complexes, [Pt(en)₂][Pt(en)₂X₂] (ClO₄)₄(X = Cl, Br, I) (HMPC's) (en=ethylenediarnine) are calculated using Maxwell equations and dipole approximation, taking into account of the ground state and odd and even charge-transfer (CT) excitons, and only one phonon is involved. The modulation mechanism is quantitatively explained by the electric-field-induced mixing between the odd and the even CT excitons. It agrees with the measured data.     

Soliton wall superlattice in the quasi-one-dimensional conductor (Per)(2)Pt(mnt)(2)

We suggest a model to explain the appearance of a high resistance high magnetic field charge-density-wave (CDW) phase, discovered by Graf et al. [Phys. Rev. Lett. 93, 076406 (2004)10.1103/PhysRevLett.93.076406] in (Per)(2)Pt(mnt)(2), where Per is perylene and mnt is maleonitriledithiolate molecules. In particular, we show that the Pauli spin-splitting effects improve the nesting properties of a realistic quasi-one-dimensional electron spectrum and, therefore, a high resistance Peierls CDW phase is stabilized in high magnetic fields. In low and very high magnetic fields, a periodic soliton wall superlattice (SWS) phase is found to be a ground state. We suggest experimental studies of the predicted phase transitions between the Peierls and SWS CDW phases in (Per)(2)Pt(mnt)(2) to discover a unique SWS phase.     

Pt纳米微粒自组装体系的电化学和原位FTIR反射光谱研究

用化学还原法制备了铂金属纳米微粒 ,透射电子显微镜 (TEM)表征纳米Pt微粒的平均直径为 2 5nm。通过二硫醇将Pt纳米微粒组装到多晶金电极表面。以Fe(CN) 4- 3-6 的氧化还原作为探针反应的电化学研究表明 ,Au表面组装二硫醇后抑制了电极 /溶液界面的电子传递过程 ,而在二硫醇上再组装铂纳米微粒后 ,电子传递又可进行。运用电化学FTIR反射光谱研究了Pt纳米微粒组装电极在酸性介质中CO的吸附 ,检测到CO的线型、桥式吸附态 ,分别在 2 0 30和 184 5cm- 1 附近给出红外吸收谱峰 ,并且有增强红外效应。此外 ,还观察到Pt纳米微粒上的CO孪生吸附态。红外吸收峰位于 2 10 0cm- 1 附近。     

NMR paramagnetic relaxation enhancement: test of the controlling influence of zfs rhombicity for S = 1

Prior theoretical work has predicted that the NMR paramagnetic relaxation enhancement (NMR-PRE) produced by electron spin S = 1 ions is highly sensitive to orthorhombic terms in the static zero field splitting (zfs) tensor. Zfs orthorhombicity (which implies chemical inequivalence of the three principal directions of the zfs-principal axis system and is described by the zfs E-parameter) is predicted to suppress the NMR-PRE profoundly relative to the reference cylindrical zfs-limit situation. This expectation was tested experimentally by a comparison of the zfs-limit NMR-PRE produced by [Ni(II)(en)(3)](2+) (en = ethylenediamine), a trigonal complex which lacks zfs-rhombicity, with the zfs-limit NMR-PRE produced by two orthorhombic complexes, [Ni(II)(en)(2)(H(2)O)(2)](2+) and [Ni(II)(en)(H(2)O)(4)](2+). As predicted, the zfs-limit NMR-PRE produced by the orthorhombic complexes in the proton resonance of a dioxane probe species in the solvent was strongly suppressed (by factors of approximately 5 and 7, respectively) relative to the comparable measurement on the trigonal complex. The suppression of the NMR-PRE due to the orthorhombic zfs terms is counteracted by an applied Zeeman field, leading to a predicted rise in the NMR-PRE with increasing Zeeman field strength; this rise occurs when the Zeeman energy is comparable to the orthorhombic zfs splitting, 2E. This second prediction of theory was likewise confirmed: the expected rhombicity-induced magnetic field dependence in the NMR-PRE was observed for the orthorhombic complexes but not for the trigonal complex.     

Thermally generated gauge singlet scalars as self-interacting dark matter

We show that a gauge singlet scalar S, with a coupling to the Higgs doublet of the form lambda(S)S+SH+H and with the S mass entirely generated by the Higgs expectation value, has a thermally generated relic density Omega(S)approximately equal to 0.3 if m(S)approximately equal to (2.9-10.5) (Omega(S)/0.3)(1/5)(h/0.7)(2/5) MeV. Remarkably, this is very similar to the range [m(S) = (6.6-15.4)eta(2/3) MeV] required in order for the self-interaction (eta/4) (S+S)(2) to account for self-interacting dark matter when eta is not much smaller than 1. The corresponding coupling is lambda(S)approximate(2.7 x 10(-10)-3.6 x 10(-9)) (Omega(S)/0.3)(2/5)(h/0.7)(4/5), implying that such scalars are very weakly coupled to the standard model sector.     

Kinetic C<Subscript>(2)-H</Subscript> exchange study of<Emphasis Type="Italic">Cis</Emphasis>-[(en)<Subscript>2</Subscript>Co(HIm)(enH)]Br<Subscript>4</Subscript> by NMR spectroscopy: Evidence for the acidity of C<Subscript>(2)-H</Subscript> proton

C_(2)-H exchange incis-[(en)₂Co(HIm)(enH)]Br₄ (Im, imidazole; en, ethylenediamine) was studied over a pD range of 9.4 to 10.2 at 60°C where thecis-[(en)₂Co(Him)(enH)]⁴⁺ andcis-[(en)₂Co(HIm)(en)]³⁺ are the species present in significant concentrations.Cis-[(en)₂Co(HIm)(enH)]⁴⁺ has pK_a1 7.86 and pK_a2 9.82 with pK_a1 corresponding to coordinated enH ionization and pK_a2 to ImH ionization. The kinetic data may be interpreted in terms of an intramolecular H-D exchange mechanism, where the “dangling”-ND₂CH₂CH₂ND₂ group acts as a base to remove the imidazole C_(2)-H proton from the coordinated DIm moiety.     

Probing outer-sphere adsorption of aqueous metal complexes at the oxide-water interface with resonant anomalous x-ray reflectivity

Resonant anomalous x-ray reflectivity near the Pt L(III) edge simultaneously revealed the geometric and spectroscopic structures of Pt(NH(3))(4)(2+) ions adsorbed at the quartz(100)-water interface. The derived Pt geometric subprofile shows two discrete "outer-sphere" adsorbed layers, and the interface-specific x-ray absorption edge profile exhibits a significant white-line enhancement compared to the bulk-solution species.     

Study of the Heterocyclic-Substituted Platinum-1,2-Enedithiolate 3ILCT Excited States by Transient Absorption Spectroscopy

The photoluminescent 1,2-enedithiolate complexes, (dppe)Pt{S₂C₂(2-quinoxaline)(H)}, [L₂Pt{S₂C₂(2-pyridinium)(H)}]⁺ where L₂ = dppm and dppe, [L₂Pt{S₂C₂(4-pyridinium)(H)}]⁺, [L₂Pt{₂C₂(N-Methyl-4-pyridinium)(H)}]⁺ and [L₂Pt{S₂C₂(CH₂CH₂-N-2-pyridinium)}]⁺ where L₂ = dppm, dppe, and dppp are room temperature dual emitters where the emissions have thiolate to heterocycle * intraligand charge transfer character (ILCT) singlet and triplet character. The pyridinium complexes have strong triplet-triplet absorption bands at approximately 400, 520 and 630 nm with a weaker band at 800 nm while (dppe)Pt{S₂C₂(2-quinoxaline)(H)} has strong triplet-triplet absorption bands at 385 and 550 nm with weaker bands at 610 and 805 nm. By fitting the decay of the transients to single exponential kinetics, the ³ILCT* lifetimes of the pyridinium complexes where determined to be 0.7 to 15.9 s (DMSO) while the ₃ILCT* lifetime of (dppe)Pt{S₂C₂(2-quinoxaline)(H)} was determined to be 2.8 s (CH₃CN). The transient absorption spectra of the complexes is affected by the appended heterocycle rather than the bulk of ancillary phosphine ligand or whether the heterocycle is protonated or alkylated.     

Microfacets of the (1 × 2) reconstructed Pt(110) surface seen in the adsorption dynamics of H2

We have detected a strong azimuth dependence of the adsorption dynamics of hydrogen on a Pt(110)(1×2) surface. Adsorption on the (1 ×2) reconstructed surface is found to be governed by the (111) microfacets of the missing row structure. Furthermore we have observed a low temperature α-state in the thermal desorption spectra comparable to the α-states for other fcc (110) surfaces.     

Formation of luminescent (NH4)2SiF6 phase from vapour etching-based porous silicon

In this paper we describe the formation of a luminescent (NH₄)₂SiF₆ via porous silicon (PS) obtained from HNO₃/HF vapour etching (VE) silicon (Si) substrates. It was found that at specific conditions, PS transforms in a luminescent thick white powder (WP) layer. Scanning electron microscopy (SEM) revealed that the WP has a coral-like structure. It was also found that PS persists as an intermediate layer between the Si substrate and the WP, and seems to be the seed that transforms into the WP. SEM microanalysis show that the WP is essentially composed of silicon (Si), nitrogen (N) and fluorine (F). Fourier transform infrared (FTIR) spectroscopy investigations show that this WP contains SiF₆²⁻ and NH₄⁺ ions and N---H chemical bonds. X-ray diffraction (XRD) patterns of the WP confirm that a (NH₄)₂SiF₆ cubic phase is concerned. SEM microanalyses show an excess of Si in the WP matrix. FTIR spectroscopy and XRD analysis reveal the presence of crystalline Si particles and SiO_x, both originating from the excess of Si. The (NH₄)₂SiF₆ WP phase emits an intense photoluminescence (PL) band, shifted towards higher energies as compared to the starting PS layer. The possible origin and mechanism of the luminescence emission was discussed taking into account the ability of small SiO_x-surrounded Si particles to emit PL at rather high energy. The wide range variation of the thickness of the (NH₄)₂SiF₆ WP may be easily used for the grooving of Si wafers.     

Anomalous Josephson current via Majorana bound states in topological insulators

We propose a setup involving Majorana bound states (MBS) hosted by a vortex on a superconducting surface of a 3D topological insulator (TI). We consider a narrow channel drilled across a TI slab with both sides covered by s-wave superconductor. In the presence of a vortex pinned to such a channel, it acts as a ballistic nanowire connecting the superconducting surfaces, with a pair of MBS localized in it. The energies of the MBS possess a 4π-periodic dependence on the superconductive phase difference φ between the surfaces. It results in the appearance of an anomalous term in the current-phase relation I(a)(φ) for the supercurrent flowing along the channel between the superconductive surfaces. We have calculated the shape of the 4π-periodic function I(a)(φ), as well as the dependence of its amplitude on temperature and system parameters.     

Zero thermal expansion in a nanostructured inorganic-organic hybrid crystal

There are very few materials that exhibit zero thermal expansion (ZTE), and of these even fewer are appropriate for electronic and optoelectronic applications. We find that a multifunctional crystalline hybrid inorganic-organic semiconductor, beta-ZnTe(en)(0.5) (en denotes ethylenediamine), shows uniaxial ZTE in a very broad temperature range of 4-400 K, and concurrently possesses superior electronic and optical properties. The ZTE behavior is a result of compensation of contraction and expansion of different segments along the inorganic-organic stacking axis. This work suggests an alternative route to designing materials in a nanoscopic scale with ZTE or any desired positive or negative thermal expansion (PTE or NTE), which is supported by preliminary data for ZnTe(pda)(0.5) (pda denotes 1,3-propanediamine) with a larger molecule.     

Photon-induced thermal desorption of CO from small metal-carbonyl clusters

Thermal CO desorption from photoexcited free metal-carbonyl clusters has been resolved in real time using two-color pump-probe photoelectron spectroscopy. Sequential energy dissipation steps between the initial photoexcitation and the final desorption event, e.g., electron relaxation and thermalization, have been resolved for Au2(CO)(-) and Pt2(CO)5-. The desorption rates for the two clusters differ considerably due to the different numbers of vibrational degrees of freedom. The unimolecular CO-desorption thresholds of Au2(CO)(-) and Pt2(CO)5- have been approximated by means of a statistical Rice-Ramsperger-Kassel calculation using the experimentally derived desorption rate constants.     

Cobalt-59 NMR and X-ray diffraction studies of hydrated and dehydrated (+/-)-tris(ethylenediamine) cobalt(III) chloride

Cobalt-59 NMR experiments have been carried out on single-crystal and polycrystalline (powder) samples of (+/-)-tris(ethylenediamine)cobalt(III) chloride trihydrate, (+/-)-[Co(en)(3)]Cl(3) x 3H(2)O, and of its dehydrate. In addition, the X-ray crystal structure of the dehydrated sample has been determined. X-ray diffraction measurements confirm a long-held assumption that dehydration has only minor effects on the structure of the [Co(en)(3)](3+) cation. Nevertheless, these small differences have a detectable effect on the 59Co nuclear magnetic resonance properties of these compounds; in particular, the nuclear quadrupole coupling constant, C(Q). Straightforward identification of the c-axis for large single crystals of (+/-)-[Co(en)(3)]Cl(3).3H(2)O and of its dehydrate allowed us to obtain single-crystal 59 Co NMR data by orienting the crystals in an MAS rotor. Data collected on single crystals and polycrystalline samples indicate that C(Q)=-3.05+/-0.05 and -2.80+/-0.05 MHz for the hydrated and dehydrated samples, respectively; the signs have been assigned on the basis of a point charge model. The chemical shift tensor principal components were also determined: for the hydrated sample, delta(perpendicular)=7281+/-2 ppm, delta(parallel)=7004+/-4 ppm and delta(iso)=7189 ppm; for the dehydrated sample, delta(perpendicular)=7288+/-2 ppm, delta(parallel)=7008+/-4 ppm and delta(iso)=7195 ppm. The electric field gradient and chemical shift tensors are axially symmetric, as required by crystal symmetry.     

Tuning the growth orientation of NiFe2O4 films by appropriate underlayer selection

We have grown NiFe₂O₄ thin films on (001)-oriented SrTiO₃ and (001)-oriented Pt underlayers. Although these two templates present a similar lattice mismatch with NiFe₂O₄ (about -6%), the ferrite grows cube-on-cube with a (001) orientation on SrTiO₃ and (111)-textured on Pt, with four different in-plane variants. This evidences that the interface energy between NiFe₂O₄ and Pt or SrTiO₃ is the key parameter ruling the film texture, while the elastic energy appears as a second-order factor. We compare the structural and magnetic properties of these two films and discuss possible applications of our findings. PACS 68.55.Jk; 75.50.Gg     

Unusual cluster shapes and directional bonding of an fcc metal: Pt/Pt(111)

Small clusters of Pt adatoms grown on Pt(111) exhibit a preference for the formation of linear chains, which cannot be explained by simple diffusion-limited aggregation. Density functional theory calculations show that short chains are energetically favorable to more compact configurations due to strong directional bonding by d(z)(2)-like orbitals, explaining the stability of the chains. The formation of the chains is governed by substrate distortions, leading to funneling towards the chain ends.     

Angular distribution patterns of photoelectrons from orbitals of CO adsorbed on Ni(100), Pt(111) and Pt(110)

The synchrotron radiation from BESSY has been used to measure the photoemission from CO orbitals adsorbed as ordered overlayers on Ni(100) c(2 × 2), Pt(111) c(4 × 2) and Pt(110) (2 × 1)p2mg. Angular distribution patterns of photoelectrons from CO orbitals were recorded with a display-type analyzer. The data were compared with differential photoionization cross sections calculated for free and oriented molecules. The results demonstrate the upright orientation of CO on Ni(100) and Pt(111), while CO on Pt(110) shows a marked difference which can be explained by assuming that the CO molecules are tilted in the [001] directions of Pt(110), yielding a (2 × 1)p2mg superstructure observed in LEED. The tilt angle is estimated to about 20°. The structure model is supported by the shape resonances of the 4σ (5σ) orbitals of CO/Pt(110) as compared to CO/Pt(111).