TGA-DTA and infrared spectra of potassium nitroprusside dihydrate: K2[Fe(CN)5NO] · 2H2O

The infrared spectra of the polycrystalline compound of the title, both normal and with different degrees of deuteration, at temperatures ranging between ca. 80 K and room temperature, were obtained. As no structural data are currently available for the compound, the assignment of the observed bands was accomplished supposing the existence of two different nitroprusside ions and, consequently, four inequivalent water molecules in the asymmetric unit, as suggested by the two bands found in the NO stretching region and the complexity observed in the water regions. TGA-DTA data are also presented and discussed.     

Mössbauer parameters of the two long-lived metastable states in Na2[Fe(CN)5NO]·2H2O single crystals

We have measured the quadrupole splitting, isomer shift and line broadening of the ground and two metastable states in Na₂[Fe(CN)₅NO]·2H₂O single crystals. Pure state II could be observed by Mössbauer spectroscopy after irradiation of state I with light in the near infrared spectral region. The difference between the two nearly infinitely long-lived electronic states is shown. A possible change of the Fe(3d, 4s, 4p) electron densities is discussed on the basis of the Mössbauer parameters and thev(FeN) andv(NO) stretching vibrations. The resulting new orbital population allows to explain the observed properties of state I. A rearrangement of the electron density due to state II would lead to a contradiction with the vibrational behaviour of the molecule. The larger line width of both metastable states could not yet be interpreted.     

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.     

ab initio Studies on Molecular Conductor (BEDSe-TTF)2[Fe(CN)5NO]

In this paper the ab initio study using pseudopotential plane wave method with the local spin density functional approximation is presented for the molecular conductor (BEDSe-TTF)₂[Fe(CN)₅NO]. The mean electronic density distributions are obtained, and we find that the extended π orbital of the selenium does not affect the properties of material as assumed in other papers and the "side-by-side" type S...S interaction is the primary interaction between donors. From band structure calculations we analyze the influence of the NO groups on the electronic structure and magnetic properties of molecule. It is shown that the itinerant electrons important to electronic properties in these types of hybrids are delocalized electrons contributed by NO groups, instead of by the 3d electrons of Fe. Additionally, we have found that the localized magnetic moment is also contributed by the NO groups in this molecular conductor. From total energy calculations the molecular structure with the lowest energy is found due to the interaction between split spins, and the particular positions of the NO groups are obtained.     

ab initio Studies on Molecular Conductor (BEDSe-TTF)2[Fe(CN)5NO]

In this paper the ab initio study using pseudopotential plane wave method with the local spin density functional approximation is presented for the molecular conductor (BEDSe-TTF)2[Fe(CN)5NO]. The mean electronic density distributions are obtained, and we find that the extended π orbital of the selenium does not affect the properties of material as assumed in other papers and the “side-by-side“ type S...S interaction is the primary interaction between donors. From band structure calculations we analyze the influence of the NO groups on the electronic structure and magnetic properties of molecule. It is shown that the itinerant electrons important to electronic properties in these types of hybrids are delocalized electrons contributed by NO groups, instead of by the 3d electrons of Fe. Additionally, we have found that the localized magnetic moment is also contributed by the NO groups in this molecular conductor. From total energy calculations the molecular structure with the lowest energy is found due to the interaction between split spins, and the particular positions of the NO groups are obtained.     

Possible reaction coordinates in the metastable states of sodiumnitroprusside Na2[Fe(CN)5NO]2H2O: a discussion based on neutron diffraction- and spectroscopic measurements

The metastable states of sodiumnitroprusside are extremely stable at temperatures below 200 K. It is possible to allocate structural changes measured by neutron diffraction to measured spectroscopic parameters, but the amount of the structural change is relatively small for a reaction co-ordinate as the metastable states have an extremely long lifetime. New hypotheses for related systems try to explain such a phenomena in two ways: The first way is a bending of the NO-bond in the metastable state, the second one an exchange of the oxygen and nitrogen atoms in the NO-bond (which can be regarded as an bending). As such changes would be possible also from our density functional calculations, we re-investigated our neutron diffraction data using the new models. However, our results are not compatible with one of these models. On the contrary, the neutron diffraction data show partially opposite tendencies. We compare both models with EXAFS measurements, with vibrational spectroscopic results and the data found by M?ssbauer spectroscopy. We propose a potential scheme for all three states (GS, and ) extracted from absorption and thermodynamic data to explain the electronic and energetic rearrangement, and the population dynamics. Received: 23 June 1997 / Accepted: 13 October 1997     

Thermal behavior and vibrational spectra of cesium nitroprusside monohydrate,Cs2[Fe(CN)5NO].H2O

The infrared spectra of the title compound in the polycrystalline state, both normal and with different degrees of deuteration, were obtained at room and low temperatures. An infrared polarized spectrum of a monocrystalline plate was also obtained as well as the Raman spectrum of the powder. The anion and water molecule vibrational bands were assigned. The data show that the anion is located in sites of C_s symmetry and that the hydration water molecule is strongly asymmetric, forming two H-bonds of different strength. TGA-DTA data on the compound are also presented.     

Mott transition and transport crossovers in the organic compound kappa-(BEDT-TTF)2Cu[N(CN)2]Cl

We have performed in-plane transport measurements on the two-dimensional organic salt kappa-(BEDT-TTF)(2)Cu[N(CN)(2)]Cl. A variable (gas) pressure technique allows for a detailed study of the changes in conductivity through the insulator-to-metal transition. We identify four different transport regimes as a function of pressure and temperature (corresponding to insulating, semiconducting, "bad metal," and strongly correlated Fermi-liquid behaviors). Marked hysteresis is found in the transition region, which displays complex physics that we attribute to strong spatial inhomogeneities. Away from the critical region, good agreement is found with a dynamical mean-field calculation of transport properties using the numerical renormalization group technique.     

Ab initio study of magnetic property of BEST2 [Fe(CN)5NO] charge-transfer salt

By means of ab initio method of the full potential linearized augmented-plane-wave, electronic band structure and its magnetic property for a charge transfer compound of bis (ethylenediselena)-tetrathiafulvalene(BEST) with [Fe(CN)₅NO] anions are investigated for the first time, where the exchange-correlation effects of electrons are accounted in the generalized gradient approximation. The spin density of states and the magnetic moment are analyzed in detail. It is found that there exists a new antiferromagnetic coupling in the organic donors because of alternating spin population in the organic donors. Besides the localized 3d electrons of Fe in [Fe(CN)₅NO] anion, the ligand nitric oxide and the cyanogen radical play important roles in the magnetic properties of the system. Our results are in good agreement with the experimental observations.     

Light-induced formation of metastable high-spin states in [Fe(mtz)6](CiO4)2

[Fe(mtz)₆](CiO₄)₂ (mtz=1-methyltetrazole) is a spin crossover compound with two different iron(II) lattice sites. Only one of them (lattice site A) shows thermally induced high spin (HS) low spin (LS) spin transition. The LIESST effect (Light-Induced Excited Spin State Trapping) can be observed below 50 K. Complex molecules in B-sites remain in HS state at all temperatures. At 20 K irradiation with red light causes a partial conversion to another HS species, HS(C), with also practically infinite lifetime.In partial fulfilment of the Ph.D. thesis.     

Mössbauer, nuclear inelastic scattering and density functional studies on the second metastable state of Na2[Fe(CN)5NO]·2H2O

The structure of the light-induced metastable state SII of Na₂[Fe(CN)₅NO]·2H₂O was investigated by transmission Mössbauer spectroscopy (TMS) in the temperature range between 85 and 135 K, nuclear inelastic scattering (NIS) at 98 K using synchrotron radiation and density functional theory (DFT) calculations. The DFT and TMS results strongly support the view that the NO group in SII takes a side-on molecular orientation and, further, is dynamically displaced from one eclipsed, via a staggered, to a second eclipsed orientation. The population conditions for generating SII are optimal for measurements by TMS, yet they are modest for accumulating NIS spectra. Optimization of population conditions for NIS measurements is discussed and new NIS experiments on SII are proposed.     

Light-induced structural changes in sodiumnitroprusside (Na2(Fe(CN)5NO)·2D2O) at 80 K

Groundstate and electronic excited state (MS_I) of deuterated sodiumnitroprusside (Na₂(Fe(CN)₅NO)·2D₂O) have been investigated by neutron diffraction as well as by optical and Mössbauer techniques. Significant structural changes occur predominantly in the O–N–Fe–C-bond. It has been shown, that the N–O bond-length is not the order parameter, as expected from other studies. We found an increase in the bond lengths Fe–N4 of 0.019(2) Å and N–O of 0.004(4) Å respectively, which is in qualitative agreement with changes determined by Raman spectroscopy and predictions based on diatomic correlations (Badger/Herschbach/Laurie). Additionally we observed a change in the Fe–C1 bond length of 0.012(3) Å in agreement with Raman meaurements.     

Nuclear-spin-lattice relaxation in the organic superconductor (BEDT-TTF)2Cu[N(CN)2]Br0.8Cl0.2

The behavior of the spin-lattice relaxation rate of ¹H nuclei in the organic superconductor (BEDT-TTF)₂Cu[N(CN)₂]Br_0.8Cl_0.2 in the temperature interval 12–319 K is investigated. A relaxation rate maximum, which depends on the resonance frequency and is associated with thermally activated vibrations of the end ethylene groups in the BEDT-TTF molecules, is observed in the vicinity of 270 K. The relaxation rate is observed to deviate from Korringa behavior at T<100 K. These deviations can be attributed to the existence of strong antiferromagnetic spin correlations. Fiz. Tverd. Tela (St. Petersburg) 39, 39–41 (January 1997)     

Magnetic quantum oscillations in the organic superconductor κ-(BEDT-TTF)2Cu[N(CN)2]Br

The interlayer magnetoresistance of the organic superconductor κ-(BEDT-TTF)₂Cu[N(CN)₂)Br is measured at ambient pressure and under pressures of up to 12.5 kbar. In addition to the slow Shubnikov-de Haas oscillations with a frequency of ≃150 T observed at P⩾5 kbar, rapid oscillations attributed to the magnetic breakdown orbit enveloping an area equal to 100% of the area of the Brillouin zone are found to emerge above B=20 T. The latter oscillations are observed at ambient pressure as well as under pressures of up to 9 kbar. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 3, 190–194 (10 August 1997) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Investigation of the metastable state of Na2[Fe(CN)5NO] · 2H2O by optical spectroscopy. II The electronic spectra of the ground and metastable states

The absorption spectra of Na₂[Fe(CN)₅NO] · 2H₂O were measured in the visible region in the range of 3400–7000 Å. In the metastable state, an additional absorption band in the long wavelength range is observed and the transition $\text{2}\text{b}{}_{\mathrm{<mtext>2</mtext>}}\text{(d}{}_{\mathrm{xy}}\text{)→}\text{7}\text{e(π}{}^1\text{?NO}\text{)}$ becomes weaker in the excited state indicating a population of the π¹(NO)-orbital. The laser excited emission spectrum shows a broad luminescence beginning at the excitation line $\text{λ =}\text{5145}\text{A}\text{?}\text{(}\text{19,436 cm}{}^{-1}\text{)}$ with a maximum at about 6250 Å (16,000 cm^-1). A strong sharp luminescence at about 7836 Å is registered and may be assigned to a transition 3b₁(d_x²?y²) or 5a₁(d_z²) to the antibonding π¹(NO)- orbital. Further the broad luminescence is superimposed by a series of sharp spikes. These sharp spikes can also be observed for several days, when the laser is switched off, and are depending on the crystal orientation.     

Infrared spectra of nitroprusside ion and its decomposition products isolated in K3[M(CN)6] (M = Fe,Co) matrices

The IR spectra of nitroprusside and of its decomposition products incorporated in potassium hexacyanometallate(III) (metal = Fe, Co) matrices has been studied. The observed multiplet structure exhibited by the nitroprusside NO stretching band in the IR spectra (covering a range of about 35 cm⁻¹) can be attributed to anisotropic host lattice effects, thus showing the sensitivity of this vibration to crystal environment.     

Proximity of the layered organic conductors alpha-(BEDT-TTF)2MHg(SCN)4 (M = K,NH4) to a charge-ordering transition

While the optical properties of the superconducting salt alpha-(BEDT-TTF)(2)-NH4Hg(SCN)(4) remain metallic down to 2 K, in the nonsuperconducting K analog a pseudogap develops at frequencies of about 200 cm(-1) for temperatures T<200 K. We show that the optical conductivity calculated with exact-diagonalization techniques on an extended Hubbard model at quarter filling is consistent with the observed low-frequency feature. We argue that the different optical responses observed are a consequence of the proximity of these compounds to a charge-ordering transition driven by the intermolecular Coulomb repulsion.     

Second Order IR Spectrum of the K4Fe(CN)6.3H2 O Crystal

The investigation of second order vibrational spectra of solid hydrates is a complicated experimental and theoretical problem. Up to new, there is a small number of IR-absorption studies and a few Raman ones, which consider multiphonon processes. Recently, the theoretical works of Agranovich^1,2 and Ruvaldis and Zawadowski³ have appear which treat some aspects of two-phonon processes in molecular crystals. The emphasis of these works is placed on some effects characteristic only for the second order spectra - Fermi resonance, two-bound states, simultaneous excitations of two molecules etc.     

Reflectivity spectra of new organic metal (BEDO-TTF)5[CsHg(SCN)4]2

The polarized reflectivity and optical conductivity spectra of microcrystals of the new organic conductor (BEDO-TTF)₅[CsHg(SCN)₄]₂ based on the donor molecule bis(ethylenedioxy)tetrathiafulvalene (BEDO-TTF) have been studied in the spectral ranges 600–6500 and 9000–40000 cm^?1 at 300 K for three principal lattice directions. The optical evidence for the quasi-two-dimensional character of the conducting electronic system is obtained. The conclusion is made that the studied crystal is the quasi-two-dimensional semimetal with overlapping electron energy bands. The basic parameters of the electronic system of the crystal are determined in the framework of the Drude model. It is found that the allowed electron energy bands of the crystal are somewhat narrower than those of the previously studied structurally allied superconductor based on the same molecule. The features of vibrational structure are identified in the σ(ω) spectra for the specified three polarizations.     

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.