Spin relaxation in the quasi-one-dimensional conductor Rb2Pt(CN)4(FHF)0.4

We analyze the electron paramagnetic resonance linewidth in Rb₂Pt(CN)₄(FHF)_0.4 as a function of temperature. Above 60 K, the results are interpreted as a superposition of spin-phonon and spin-spin relaxation effects. The dominant contribution to the relaxation rate l/T₂ has a dipolar origin in contrast to the spin-phonon origin observed in K₂Pt(CN)₄Br_0.3 · H₂O. This difference could arise from different anisotropy ratios of the transfer integrals. The influence of the interchain coupling is also discussed.     

High pressure tuning of optical transitions in Mg[Pt(CN)4]·7H2O

Mg[Pt(CN)₄]·7H₂O belongs to the class of tetracyanoplatinates(II) which crystallize in columnar structures. In different M_x[Pt(CN)₄]·yH₂O (MCP) single crystals the in-chain Pt-Pt-distance R varies between 3.67 Å (NaCP) and 3.15 Å (MgCP). Two optical transitions can be observed in polarized emission with the electric field vector E either parallel or perpendicular to the columnar (c)-axis. Polarized emission spectra of MgCP are recorded under hydrostatic pressure up to p ≈ 18 kbar (at 295 K). The transition energy v?₆ can be tuned from 17,600 cm^-1 to about 12,000 cm^-1 (2.18-1.48 eV). The pressure induced red shift for the two transitions is: E 6 c: dv?₆/dp = -320±20 cm^-1/kbar, E ⊥ c: dv?_⊥/dp = -270±20 cm^-1/kbar. These values are discussed in the context of the known functional relationship (for ambient conditions) between v? and R.     

Electrical conduction studies on one-dimensional Cs2[Pt(CN)4](FHF)0.39 and Rb2[Pt(CN)4](FHF)0.40

Variable temperature (300-40 K) 4-probe d.c. conduction studies on Cs₂[Pt(CN)₄](FHF)_0.39 and Rb₂[Pt(CN)₄](FHF)_0.40 are described. In these salts T_3D occurs at a lower temperature than in K₂[Pt(CN)₄]Br_0.3·3H₂O and this is attributed to the absence of an inter-chain network of hydrogen bonded water molecules in the bifluorides.     

Adsorption and decomposition of H2O on a K-covered Pt(111) surface

The adsorption of H₂O on clean and K-covered Pt(111) was investigated by utilizing Auger, X-ray and ultra-violet photoemission spectroscopies. The adsorption on Pt(111) at 100–150 K was purely molecular (ice formation) in agreement with previous work. No dissociation of this adsorbed H₂O was noted on heating to higher temperatures. On the other hand, adsorption of H₂O on Pt(111) + K leads to dissociation and to the formation of OH species which were characterized by a work function increase, an O 1s binding energy of 530.9 eV and UPS peaks at 4.7 and 8.7 eV below the Fermi level. The amount of OH formed was proportional to the K coverage for θ_K > 0.06 whereas no OH could be detected for θ? 0.06. Dissociation of H₂O occurred already at T = 100 K, with a sequential appearance of O 1s peaks at 531 and 533 eV representing OH and adsorbed H₂O, respectively. At room temperature and above only the OH species was observed. Annealing of the surface covered with coadsorbed K/OH indicated the high stability of this OH species which could be detected spectroscopically up to 570 K. The adsorption energy of H₂O coadsorbed with K and OH on Pt(111) is increased relative to that of H₂O on Pt. The work function due to this adsorbed H₂O increases whereas it decreases for H₂O on Pt(111). The energy shifts of valence and O1s core levels of H₂O on Pt + K as deduced from a comparison of gas phase and adsorbate spectra are 2.8–4.2 eV compared to ≈ 1.3–2.3 eV for H₂O on Pt (111). This increased relaxation energy shift suggests a charge transfer screening process for H₂O on Pt + K possibly involving the unoccupied 4a₁ orbital of H₂O. The occurrence of this mode of screening would be consistent with the higher adsorption energy of H₂O on Pt + K and with its high propensity to dissociate into OH and H.     

Experimental and theoretical study of dicyanocarbene C(CN)2

Dicyanocarbene C(CN)₂ and its radical cation (m/z 64) were generated by dissociative ionization of tetracyanoethene, dicyanofuroxan and dicyanofurazan and characterized by collisional activation (CA) and neutralization-reionization (NR) mass spectrometries and tandem MS³ experiments performed in a ‘hybrid’ tandem mass spectrometer having a sector-quadrupole-sector configuration. In both neutral and ionized forms, dicyanocarbene is found to be a stable and detectable species. Existence of the peaks at m/z 52, 24 and 12 in the CA/NR spectra suggests however some possible post-collisional rearrangements. The carbene was further studied by ab initio calculations using B3LYP/6-311+G(3df) for geometries and CASPT2(14,12) and MR-SDCI with the cc-pVTZ and aug-cc-pVTZ basis sets for relative energies. The dicyano form NC-C-CN is consistently more stable than its isocyano isomers CN-C-CN and CN-C-NC, irrespective of the electronic state. Each neutral carbene exhibits a triplet ground state lying up to 2.6 eV below the singlets. All the triplet, singlet and ionized states of dicyanocarbene have a linear shape. The other states have either linear or bent shape but small barriers to linearity. Adiabatic ionization energies (IE_a) were estimated as follows: NC-C-CN: 11.3 eV with linear ²Π_u cation; NC-C-NC: 10.4 eV with linear ²Π cation, and CN-C-NC: 9.9 eV with bent ²A₁ cation.     

Coordination of acetonitrile (CH3CN) to platinum (111): Evidence for an η2(C,N) species

Acetonitrile (CH₃CN) coordination to a Pt(111) surface has been studied with electron energy loss vibrational spectroscopy (EELS), XPS, thermal desorption and work function measurements. We compare data for the surface states with known acetonitrile coordination complexes. For CH₃CN adsorbed on Pt(111) at 100 K, the molecule is rehybridized and adsorbs with the CN bond parallel or slightly inclined to the surface plane in an η²(C, N) configuration. The ν(CN) frequency is 1615 cm^?1 and the C ls and N ls binding energies are 284.6 eV and 397.2 eV respectively. By contrast, weakly adsorbed multilayer acetonitrile exhibits a ν(CN) vibrational frequency of 2270 cm^?1, and C ls and N ls binding energies of 286.9 eV and 400.1 eV respectively. Both the EELS and XPS results are consistent with rehybridization of the CN triple bond to a double bond with both C and N atoms of the CN group attached to the surface. In addition to this majority η²(C, N) monolayer state, evidence is found for a second, more strongly bound minority molecular state in thermal desorption spectra. As a result of the low coverage of this state, EELS was unable to spectroscopically identify it and we tentatively assign it as an η⁴(C, N) species associated with accidental step sites. By contrast to the surface complexes, almost all of the known platinum-nitrile coordination complexes are end-bonded via the N lone-pair orbital. Several cases of side-on bonding are known, however, and we compare the results with the known complex Fe₃(η²-NCCH₃)(CO)₉. The difference in the coordinative properties of a Pt(111) surface versus a single Pt atom must be due to the increased ability of multi-atom arrays to back-donate electrons into the π¹ system of acetonitrile. Previously published EELS and XPS results for monolayer acetonitrile on Ni(111) and polycrystalline films are almost identical to the present results on Pt(111). We believe that the monolayer of $\text{CH}{}_3\text{CN}\text{Ni}\text{(111)}$ is also an η²(C, N) species, not an end-bonded species previously proposed by Friend, Muetterties and Gland.     

Analternative model for the conductivity behavior of K2Pt(CN)4Br0.3·3H2O

It is shown that the reordering of the bromine atoms into a new cubic lattice at low temperatures can produce the changes observed in the conductivity behavior of the mixed valence salt K₂Pt(CN)₄Br_0.32·3H₂O. The optical data are examined in terms of an RPA calculation of the dielectric response of the crystal and it is noted that a periodic potential can reproduce the observed structure in the imaginary part without the need for identifying the charge carriers.     

掺有浅电子陷阱的AgCl微晶的光电子衰减谱的时间分辨特性

利用微波吸收技术研究了K4Ru(CN)6浅电子陷阱掺杂剂对立方体AgCl微晶光生电子时间分辨特性的影响。结果表明,掺杂剂的掺杂量以及掺杂位置对乳剂的光生电子时间分辨特性都有影响。掺杂量为245×10-5mol·(molAg)-1,掺杂位置75%Ag时自由电子的衰减最慢,寿命最长。     

Study by X-ray crystallography and Mössbauer spectroscopy of CeFe(CN)6·5H2O and GdFe(CN)6·4H2O

From the X-ray crystallographic point of view, the environment of Fe in CeFe(CN)₆·5H₂O has higher octahedral symmetry than that in GdFe(CN)₆·4H₂O. The single Mössbauer absorption peak for CeFe(CN)₆·5H₂O indicates that the three t_2g levels are close to each other in energy due to a near-perfect octahedral Fe(CN)₆ unit. The doublet peak of of GdFe(CN)₆·4H₂O can be explained by assuming that the three t_2g levels are widely separated as a result of the distortion of the octahedral Fe(CN)₆ unit.     

Thermal expansion of the one-dimensional conductor K2Pt(CN)4Br0.3·xH2O and K2Pt(CN)4·xH2O

Measurements of the thermal expansion coefficients of K₂Pt(CN)₄Br_0.3· xH₂O and K₂Pt(CN)₄·xH₂O show a large anisotropy of the a-and c- directions. Their temperature dependence could be described by a simple Grüneisen theory. In the range from 80–330°K no anomaly indicating a Kohn-Peierls transition could be found.     

Inelastic neutron scattering from the quasi-one-dimensional conductor K1.75[Pt(CN)4]·1.5H2O

Neutron inelastic scattering has been used to study the longitudinal and one of the transverse acoustic phonons, propagating along the [001]¹ direction in triclinic K_1.75[Pt(CN)₄]·1.5H₂O. This material appears to be a quasi-one-dimensional conductor, with a commensurate distortion. We observe a reasonably well defined Kohn anomaly, which shows little temperature dependence between 80 and 300 K.     

CO stretching vibrations on Pt(111) and Pt(110) studied by sumfrequency generation

Optical sum-frequency generation (SFG) is used to characterize CO stretching vibrations on Pt(111) and Pt(110) surfaces. Different adsorption sites (terminal, bridge and step sites) are identified in the SFG spectra of CO on Pt(111), in good quantitative agreement with previous infrared reflection-absorption experiments on this system. For CO on Pt(110) we only observe CO molecules on terminal sites. The measured CO stretching vibration frequencies on Pt(110), both for low and high coverages, are at variance with the results of previous infrared studies. Our SFG results for CO on Pt(110) are confirmed by independent EELS measurements which, in addition, also reveal the frustrated rotational mode and the metal-CO vibration. The measured frequency of 2065 cm⁻¹ for low CO coverage on Pt(110)-(1 × 2) is consistent with a previously proposed empirical relation between the frequency of an isolated adsorbed CO molecule and the coordination number of the binding Pt surface atom.     

Electron energy loss spectrum of cyanogen on Pt (100)

Electron energy loss spectra for adsorbed cyanogen on Pt(100) are presented, and discussed in terms of possible models suggested by other techniques. Adsorbate induced loss features are found at 11 and 14 eV, and these are associated with levels below the Fermi level as observed in ultra-violet photoemission. As in the case of CO adsorption losses in the adsorbed phase occur at energies significantly larger than in the gas phase, indicating an upward shift of the final 2π¹ state due to mixing with metal orbitais. Thermal desorption studies of C₂N₂ on Pt clearly resolve α and β phases, but there is some controversy over whether the β phase involves mainly single CN units bonding to the metal, whether C₂N₂ is molecularly adsorbed, or whether paracyanogenlike structures form at the surface. The electron spectroscopic evidence is examined, and is shown on balance to support adsorption in some molecular form.     

High pressure cyanide exchange study on a square-planar tetracyanometalate complex of Pt(II)

Abstract

Previous studies of cyanide exchange on square planar tetracyanoplatinate complex [Pt(CN)₄]^2- have been undertaken only at a high pH. For a more complete fundamental understanding of this system we extended the investigations of these exchanges over a large pH range. NMR kinetics methods (magnetisation transfer, isotopic exchange) proved to be very useful for obtaining quantitative rate data of the cyanide exchange on this complex. In fact it is quite significant that the reactivity of this metal center spans a ca. 9-order of magnitude range as a function of pH.

Variable temperature and variable pressure studies were undertaken in aqueous solutions and the following activation parameters obtained: ΔH? = (25.1 ± 0.4) kJmol^?1 and activation entropy ΔS? = -(142±2)JK^?1mol^?1 and activation volume ΔV? = -(27±2)cm³mol^?1.     

Vibrational dynamics of the CN stretching mode of [Ru(CN)_6]~(4-) in D_2O studied by nonlinear infrared spectroscopy

We have studied vibrational dynamics of the T1u mode of the CN stretching mode of [Ru(CN)6 ]4- in D2O by infrared(IR) nonlinear spectroscopy such as an IR three-pulse photon echo experiment and polarization-sensitive IR pump-probe spectroscopy. The isotropic component of the pump-probe signal shows a bi-exponential decay with time constants of 0.8 ps and 20.8 ps. The fast and slow components correspond to the rapid equilibration between the T1u mode and the Raman active modes of the CN stretching mode and the vibrational population relaxation from the v=1 state of the T1u mode,respectively. Anisotropy of the pump-probe signal decays with a time constant of 3.1 ps,which is due to the time evolution of the superposition states of the triply degenerate T1u modes. Three pulse photon echo measurements showed that the time correlation function of the frequency fluctuation decays bi-exponentially with time constants of 80 fs and 1.4 ps. These time constants depend only on the solute and are independent of the solvent,whereas the amplitudes depend on both the solute and solvent.     

Ultrafast hot-electron dynamics observed in Pt( -)(3) using time-resolved photoelectron spectroscopy

Time-resolved two-photon photoelectron spectra have been measured for free Pt( -)(3) using femtosecond pulses of 1.5 eV photon energy in a pump-probe configuration. The time-dependent photoelectron distribution reveals a lifetime of optically excited states of less than 70 fs. Such an unexpected fast electron relaxation in Pt( -)(3) suggests the existence of inelastic electron-electron scattering processes in a triatomic cluster which result in a lifetime similar to those of bulk metals.     

Synthesis,structure and preliminary results on electrical and magnetic properties of (Perylene)2 [Pt(mnt)2]

In this paper we report the preparation, crystal structure and some physical properties of the conducting molecular (Perylene)₂ [Pt(S₄C₄(CN)₄)].The crystal structure consists of segregated stacks of perylene and Pt S₄C₄ (CN)₄ units, with a spacing of 3.3 Å between the carbon atoms in the perylenes. The temperature dependence of the electrical conductivity is metallic with a maximum at approximately 15 K. At this temperature a sharp transition to an insulating state occurs. Magnetic suceptibility measurements confirm the existence of a transition in this temperature range.     

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。     

High‐pressure studies of the micro‐Raman spectra of iron cyanide complexes: Prussian blue (Fe4[Fe(CN)6]3), potassium ferricyanide (K3[Fe(CN)6]), and sodium nitroprusside (Na2[Fe(CN)5(NO)]·2H2O)

The pressure dependences of the peaks observed in the micro‐Raman spectra of Prussian blue (Fe₄[Fe(CN)₆]₃), potassium ferricyanide (K₃[Fe(CN)₆]), and sodium nitroprusside (Na₂[Fe(CN)₅(NO)]·2H₂O) have been measured up to 5.0 GPa. The vibrational modes of Prussian blue appearing at 201 and 365 cm⁻¹ show negative dν/dP values and Grüneisen parameters and are assigned to the transverse bending modes of the Fe C N Fe linkage which can contribute to a negative thermal expansion behavior. A phase transition occurring between 2.0 and 2.8 GPa in potassium ferricyanide is shown by changes in the spectral region 150–700 cm⁻¹. In the spectra of the nitroprusside ion, there are strong interactions between the FeN stretching mode and the FeNO bending and the axial CN stretching modes. The pressure dependence of the NO stretching vibration is positive, 5.6 cm⁻¹ GPa⁻¹, in contrast to the negative behavior in the iron(II)‐meso‐tetraphenyl porphyrinate complex. Copyright © 2011 John Wiley & Sons, Ltd.     

Role of surface elastic relaxations in an O-induced nanopattern on Pt(110)-(1 x 2)

Scanning tunneling microscopy shows that a nanopattern forms as the Pt(110)-(1 x 2) surface is exposed to oxygen at room temperature or above. The nanopattern consists of [11[over]0] oriented O-induced stripes assembling into a (11 x 2) superstructure at high O coverage. The stripes form because the O adsorption energy increases by expanding the Pt lattice along the ridges of the surface as compared to the bulk. From interplay with density functional theory calculations, we show that the O-induced nanoscale periodicity is caused by short-ranged elastic relaxations confined to the surface.