We investigated the effects of paramagnetic (PM) fluctuations on the thermochemistry of the MnO(100) surface in the oxygen evolution reaction (OER) using the "noncollinear magnetic sampling method \textit{plus} $U$" (NCMSM$+U$). Various physical properties, such as the electronic structure, free energy, and charge occupation, of the MnO (100) surface in the PM state with several OER intermediates, were reckoned and compared to those in the antiferromagnetic (AFM) state. We found that PM fluctuation enhances charge transfer from a surface Mn ion to each of the intermediates and strengthens the chemical bond between them, while not altering the overall features, such as the rate determining step and resting state, in reaction pathways. The enhanced charge transfer can be attributed to the delocalized nature of valence bands observed in the PM surface. In addition, it was observed that chemical-bond enhancement depends on the intermediates, resulting in significant deviations in reaction energy barriers. Our study suggests that PM fluctuations play a significant role in the thermochemistry of chemical reactions occurring on correlated oxide surfaces.
Using a combination of single-crystal neutron scattering and reverse Monte Carlo refinements, we study the magnetic structure of paramagnetic MnO at a temperature (160\,K) substantially below the Curie-Weiss temperature $|θ|\sim550$\,K. The microscopic picture we develop reveals a locally-ordered domain structure that persists over distances many times larger than the correlation length implied by direct analysis of the spin correlation function. Moreover, the directional dependence of paramagnetic spin correlations in paramagnetic MnO differs in some important respects from that of its incipi…
We present a new approach based on the static density functional theory (DFT) to describe paramagentic MnO, which is a representative paramagnetic Mott insulator. We appended the spin noncollinearity and the canonical ensemble to the magnetic sampling method (MSM), which is one of the supercell approaches based on disordered local moment model. The combination of the noncollinear MSM (NCMSM) with DFT$+U$ represents a highly favorable computational method called NCMSM$+U$ to accurately determine the paramagnetic properties of MnO with moderate numerical cost. The effects of electron correlation…
Temperature and current dependences of resistivity of bulk La$_{0.75}$Ca$_{0.25}$MnO$_{3}$ sample grown by the floating-zone method were studied using single ramp pulses of current. It is found that near the Curie temperature $T_C$ the sample resistance depends substantially on current magnitude. The observed features can be determined by inhomogeneous Joule overheating due to mixed phase state of manganites near the ferromagnetic-paramagnetic transition and percolation character of this transition.
Metallic transition-metal oxides undergo a metal-to-insulator transition (MIT) as the film thickness decreases across a ritical thickness of several monolayers (MLs), but its driving mechanism remains controversial. We have studied the thickness-dependent MIT of the ferromagnetic metal La$_{0.6}$Sr$_{0.4}$MnO$_3$ by x-ray absorption spectroscopy and x-ray magnetic circular dichroism. As the film thickness was decreased across the critical thickness of the MIT (6-8 ML), a gradual decrease of the ferromagnetic signals and a concomitant increase of paramagnetic signals were observed, while the Mn…
The ultrasonic properties of La$_{1-x}$Ca$_{x}$MnO$_{3}$ ($x\approx 0.25$) with the Curie temperature $T_C$ about 200 K are studied. Temperature dependences of longitudinal and transverse sound velocities were measured in zero magnetic field and for different constant magnetic fields as well. The ultrasonic study is supported by magnetic, resistive, magnetoresistive, structural and other measurements of the sample that facilitate interpretation of the results obtained. The magnetic field influence on sound properties found in this study presents some new features of the interplay between the e…
A band structure description of the observed large band gaps and moments in both the antiferromagnetic (AFM) and paramagnetic (PM) phases of the classic NaCl-structure Mott insulators MnO, FeO, CoO, and NiO is provided by ordinary, single-determinant density functional theory method. As noted by previous authors, the ordered AFM phases already show in band theory significant band gaps. However, for the disordered PM phases the commonly used band model has been to assume the macroscopically observed, averaged NaCl structure, where all transition metal sites are forced to be symmetry-equivalent …
Raman scattering experiments have been carried out on single crystals of Nd$_{0.5}$Sr$_{0.5}$MnO$_3$ as a function of temperature in the range of 320-50 K, covering the paramagnetic insulator-ferromagnetc metal transition at 250 K and the charge-ordering antiferromagnetic transition at 150 K. The diffusive electronic Raman scattering response is seen in the paramagnetic phase which continue to exist even in the ferromagnetic phase, eventually disappearing below 150 K. We understand the existence of diffusive response in the ferromagnetic phase to the coexistence of the different electronic pha…
^{139}La NMR measurements of La_{2/3}Ca_{1/3}MnO_3 performed in the paramagnetic state and high magnetic fields are reported. Analysis of the high temperature spectrum measured establishes that the spectrum it is a standard powder pattern broadened by a variation in lattice distortions. At lower temperatures, the spectrum shifts and broadens. Both the shift and broadening exhibit Curie-Weiss behavior, indicating that the shift measures the polarization of the electron spin system, and the broadening reflects a distribution of magnetic susceptibilities. This distribution may result from variati…
Sm{0.5-x}Pr{x}Sr{0.5}MnO{3} exhibits variety of ground states as x is varied from 0 to 0.5. At an intermediate doping of x = 0.3 a charge-ordered CE type antiferromagnetic insulating (AFI) ground state is seen. The transition to this ground state is from a paramagnetic insulating (PMI) phase through a ferromagnetic metallic phase (FMM). Local structures in PMI and AFI phases of x = 0.3 sample have been investigated using Pr K-edge and Sm K-edge Extended X-ray Absorption Fine Structure (EXAFS). It can be seen that the tilting and rotation of the MnO6 octahedra about the b-axis are responsible f…
Temperature-dependent Brillouin scattering studies have been carried out on La_{0.77}Ca_{0.23}MnO_3 across the paramagnetic insulator - ferromagnetic metal (I-M) transition. The spectra show a surface Rayleigh wave (SRW) and a high velocity pseudo surface acoustic wave (HVPSAW) besides bulk acoustic waves (BAW). The Brillouin shifts associated with SRW and HVPSAW show blue-shifts, where as the frequencies of the BAW decrease below the I-M transition temperature (T_C) of 230 K. These results can be understood based on the temperature dependence of the elastic constants. We also observe a centra…
We discuss the effects of local structure on the electrical transport and magnetic properties of La(0.67)Ca(0.33)Mn(1-x)Ti(x)O(3) system.Based on the intercomparison of the structure, transport and magnetic properties of the Mn site substituted La(0.67)Ca(0.33)MnO(3) with isovalent diamagnetic and paramagnetic ions, we argue that local structural effects have a decisive role to play, compared to the local spin coupling effects, in the ferromagnetic-metallic ground state of the CMR manganites
We report the occurrence of both \emph{ab} and \emph{bc} cycloidal ordering of Mn-spins at different temperatures and their possible coexistence at low temperatures in the polycrystalline mixed rare-earth compounds, \emph{R}$_{0.5}$Dy$_{0.5}$MnO$_3$ (\emph{R} = Eu and Gd), which exhibit extraordinary magnetoelectric properties. While the polarization of Gd$_{0.5}$Dy$_{0.5}$MnO$_3$ is comparable to TbMnO$_3$, the compound Eu$_{0.5}$Dy$_{0.5}$MnO$_3$ shows high value of polarization. However, both of them show giant magnetic tunability and exhibit large magnetocapacitance whose sign changes acro…
The valence band electronic structure of Pr$_{0.5}$Sr$_{0.5}$MnO$_3$ has been investigated across its paramagnetic metallic (PMM) - ferromagnetic metallic (FMM) - antiferromagnetic insulator (AFMI) transition. Using surface sensitive high resolution photoemission we have conclusively demonstrated the presence of a pseudogap of magnitude 80 meV in the near Fermi level electronic spectrum in the PMM and FMM phases and finite intensity at the Fermi level in the charge ordering (CO)-AFMI phase. The pseudogap behavior is explained in terms of the strong electron-phonon interaction and the formation…
We prospect magneto-dielectricity in $La_{0.53}Ca_{0.47}MnO_{3}$ across its paramagnetic (PMI) to ferromagnetic (FMM) isostructural transition at $T_{C} \sim 253K$, by magnetic ($(M)$), caloric ($(W)$), dielectric ($(ε')$), magneto-resistive (MR), and magneto-capacitance (MC) investigations. Skew-broadened first-order transition character is confirmed via heating/cooling hystereses in $(M)(T)$ and $(W)(T)$, with superheating temperature $T**$ almost next to $T_C$ and supercooling temperature $T*$ exhibiting kinetics. Above $T_C$, linearly-related MC and MR reflect purely magneto-resistance eff…
We study combined effect of hydrostatic pressure and magnetic field on the magnetization of La${_{0.5}}$Ca${_{0.5}}$MnO${_{3}}$. We do not observe any significant effect of pressure on the paramagnetic to ferromagnetic transition. However, pressure asymmetrically affects the thermal hysteresis across the ferro-antiferromagnetic first-order transition, which has strong field dependence. Though the supercooling (T*) and superheating (T**) temperatures decrease and the value of magnetization at 5K (M$_{5K}$) increases with pressure, T* and M$_{5K}$ shows abrupt changes in tiny pressure of 0.68kba…
High real-space-resolution atomic pair distribution functions of La_(1-x)Ca_(x)MnO_3 (x=0.12, 0.25 and 0.33) have been measured using high-energy x-ray powder diffraction to study the size and shape of the MnO_6 octahedron as a function of temperature and doping. In the paramagnetic insulating phase we find evidence for three distinct bond-lengths (~ 1.88, 1.95 and 2.15A) which we ascribe to Mn^{4+}-O, Mn^{3+}-O short and Mn^{3+}-O long bonds respectively. In the ferromagnetic metallic (FM) phase, for x=0.33 and T=20K, we find a single Mn-O bond-length; however, as the metal-insulator transiti…
We report an infrared reflection spectroscopy study of La$_{1/2}$Ca$_{1/2}$MnO$_3$ over a broad frequency range and temperature interval which covers the transitions from the high temperature paramagnetic to ferromagnetic and, upon further cooling, to antiferromagnetic phase. The structural phase transition, accompanied by a ferromagnetic ordering at T$_C$=234 K, leads to enrichment of the phonon spectrum. A charge ordered antiferromagnetic insulating ground state develops below the Néel transition temperature T$_N$=163 K. This is evidenced by the formation of charge density waves and opening …
Perovskite-type manganites, which are well-known for their intriguing physical properties such as colossal magnetoresistance (CMR) and half metalicity, have been considered as candidate materials for spintronics. However, their ferromagnetic (FM) properties are often suppressed in thin films when the thickness is reduced down to several monolayers (MLs). In order to investigate how the magnetic phases evolve near the paramagnetic (PM)-to-FM phase transition boundary, we have performed temperature-dependent x-ray magnetic circular dichroism (XMCD) experiments on a La$_{1-x}$Sr$_{x}$MnO$_3$ (LSM…
Nanowires of Pr_0.57 Ca_0.41 Ba_0.02 MnO_3 (PCBM) (diameter ~ 80-90 nm and length ~ 3.5 mm) were synthesized by a low reaction temperature hydrothermal method. Single-phase nature of the sample was confirmed by XRD experiments. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the morphology and microstructures of the nanowires. While the bulk PCBM is known to exhibit charge order (CO) below 230 K along with a ferromagnetic transition at 110 K, SQUID measurements on the nanowires of PCBM show that the charge order is completely absent and a…
Charge transfer induced interfacial ferromagnetism and its impact on the exchange bias effect in La$_{0.7}$Sr$_{0.3}$MnO$_3$/NdNiO$_3$ correlated oxide heterostructures were investigated by soft x-ray absorption and x-ray magnetic circular dichroism spectra in a temperature range from 10 to 300 K. Besides the antiferromagnetic Ni$_3^+$ cations which are naturally part of the NdNiO$_3$ layer, Ni$_2^+$ ions are formed at the interface due to a charge transfer mechanism involving the Mn element of the adjacent layer. They exhibit a ferromagnetic behavior due to the exchange coupling to the Mn$_4^…
The effect of deposition oxygen pressure (P$_{O}$) on phase separation (PS) induced in epitaxial La$_{0.67}$Ca$_{0.33}$MnO$_{3}$/NdGaO$_{3}$(001) films was investigated. Fully oxygenated films grown at high P$_{O}$ are anisotropically strained. They exhibit PS over a wide temperature range, because of the large orthorhombicity of NdGaO$_{3}$ substrates. The paramagnetic insulator-to-ferromagnetic metal (FM) and FM-to-antiferromagnetic insulator (AFI) transitions gradually shift to lower temperatures with decreasing PO. The AFI state is initially weakened (P$_{O}$ >= 30 Pa), but then becomes mo…
We have studied the chemical potential shift and changes in the electronic density of states near the Fermi level ($E_F$) as a function of carrier concentration in Pr$_{1-x}$Ca$_x$MnO$_3$ (PCMO, $0.2 \le x \le 0.65$) through the measurements of photoemission spectra. The results showed that the chemical potential shift was suppressed for $x \agt 0.3$, where the charge exchange (CE)-type antiferromagnetic charge-ordered state appears at low temperatures. We consider this observation to be related to charge self-organization such as stripe formation on a microscopic scale in this composition ran…
We have investigated the effect of Ti doping on the transport properties coupled with the magnetic ones in Sm$_{0.55}$Sr$_{0.45}$Mn$_{1-η}$Ti$_η$O$_3$ ($0 \leq η\leq 0.04$). The parent compound, Sm$_{0.55}$Sr$_{0.45}$MnO$_3$, exhibits a first-order paramagnetic-insulator to ferromagnetic-metal transition just below $T_{\rm c}$ = 128 K. With substitution of Ti at Mn sites ($B$-site), $T_{\rm c}$ decreases approximately linearly at the rate of 22 K$\%^{-1}$ while the width of thermal hysteresis in magnetization and resistivity increases almost in an exponential fashion. The most spectacular effe…
The nature of phase separation in $Pr_{0.5}Sr_{0.5}MnO_3$ has been probed by linear as well as nonlinear magnetic susceptibilities and resistivity measurements across the 2nd order paramagnetic to ferromagnetic transition ($T_C$) and 1st order ferromagnetic to antiferromagnetic transition ($T_N$). We found that the ferromagnetic (metallic) clusters, which form with the onset of long-range order in the system at $T_C$, continuously decrease their size with the decrease in temperature and coexist with non-ferromagnetic (insulating) clusters. These non-ferromagnetic clusters are identified to be …
Of the perovskites, ABX_<3>, a subset of special interest is the family in which the A site is occupied by a lanthanide ion, the B site by a rare earth and X is oxygen, as such materials often exhibit a large change in electrical resistance in a magnetic field, a phenomenon known as "colossal" magnetoresistance (MR). Two additional phenomena in this family have also drawn attention: the metal-insulator transition (MIT) and electroresistance (ER). The MIT is revealed by measuring resistance as a function of temperature, and observing a change in the sign of the gradient. ER - the dependence of …
We have studied the temperature dependence of the photoemission spectra of Pr$_{1-x}$Ca$_x$MnO$_3$ (PCMO) with $x=0.25$, 0.3 and 0.5. For $x=0.3$ and 0.5, we observed a gap in the low-temperature CE-type charge-ordered (CO) phase and a pseudogap with a finite intensity at the Fermi level ($E_F$) in the high-temperature paramagnetic insulating (PI) phase. Within the CO phase, the spectral intensity near $E_F$ gradually increased with temperature. These observations are consistent with the results of Monte Carlo simulations on a model including charge ordering and ferromagnetic fluctuations [H. …
The 'two-electron' doped rare earth mangnites Ca_1-x Ce_x MnO_3 (x = 0.1,0.2) are probed using resistivity, ac susceptibility and electron paramagnetic resonance (EPR) measurements across their respective charge ordering (CO) temperatures T_CO = 173 K and 250 K. The EPR 'g' factor and intensity as well as the transport and magnetic behaviours of the two compositions are qualitatively similar and are as expected for CO systems. However, the EPR linewidth, reflective of the spin dynamics, for x = 0.1, shows a strongly anomalous temperature dependence, decreasing with decreasing temperature below…
