The document summarizes research on the effects of electric fields on transition metal ions in iron- and copper-based superconductors. First-principles calculations using DFT, GGA+U, and HSE methods were performed on four iron-based and four copper-based superconductors. It was found that under electric fields, the electron clouds of Fe ions rotate rigidly rather than deforming elastically. This suggests a possible new mechanism of superconducting electron pairing via rotation of transition metal ion electron clouds induced by electric fields.
Vacancy and Copper-doping Effect on Superconductivity for Clathrate MaterialsYang Li
We present a joint experimental and theoretical study of the superconductivity and electronic structures in type-I Cu-doped silicon clathrates and germanium clathrates. The superconducting critical temperature in Ba8Si46–xCux is shown to decrease strongly with copper content increasing. These results are corroborated by CASTEP approach, first-principles simulations calculated from the density-functional theory with plane waves and pseudopotentials. The simulations show that Cu-doping results in a large decrease of electronic density of states in Fermi level, which can explain the superconducting critical temperature decrease with Cu-doping in the BCS theoretical frame. Further, comparison of Ba8Ge46 and Ba8Si46 within the CASTEP approach shows that the superconductivity is an intrinsic property of the sp3 silicon and germanium clathrates without vacancy in the cage framework. By analysis of the density of states (DOS) and reported experimental results of the Zintl-like Ba8Ge43, a new mechanism of vacancy defect is suggested to explain the absence of superconductivity in Ge clathrates, which is of benefit to eliminating the divarication between theoretical prediction and the experimental observation for superconductivity in Ge clathrates. Keeping an entire Si and Ge cage structure without vacancy is the prerequisite for occurrence of superconductivity in clathrates.
Solid-state electrolytes exhibit good safety and stability, and are promising to replace current organic liquid electrolytes in rechargeable battery applications. In this talk, we will present our efforts at developing scalable first principles techniques to design novel solid-state electrolytes. Using the recently discovered Li10GeP2S12 lithium super ionic conductor as an example, we will discuss how various properties of interest in a solid-state electrolyte can be predicted using first principles calculations. We will show how the application of these first principles techniques has suggested two chemical modifications, Li10SiP2S12 and Li10SnP2S12, that retains the excellent Li+ conductivity of Li10GeP2S12 at a significantly reduced cost. These modifications have recently been synthesized, and the measured Li+ conductivities are in excellent agreement with our first principles predictions. We will conclude with a demonstration of how relatively expensive first principles calculations can be intelligently scaled and combined with topological analysis to be a useful screening tool for novel solid-state electrolytes.
In recent years, there have been great interest in alkali-O2 batteries with extremely high specific energies. Li-O2 batteries offer the greatest theoretical specific energy, but currently suffer from large charging overpotentials and low power densities. Na-O2 offers a somewhat lower theoretical specific energy compared to Li-O2, but still a substantial improvement over today’s lithium-ion batteries. In this talk, we will demonstrate how first principles calculations can provide crucial insight into the workings of alkali-O2 batteries. We will elucidate a facile mechanism for recharging Li2O¬¬2 that is accessible at relatively low overpotentials of ~0.3-0.4V and is likely to be kinetically favored over Li2O2 decomposition. We will also demonstrate that sodium superoxide (NaO2) is predicted to be considerably more stable than sodium peroxide (Na2O2) at the nanoscale. Using first principles calculations, we derive the specific electrochemical conditions to nucleate and retain NaO2 and comment on the importance of considering the nanophase thermodynamics when optimizing an electrochemical system.
Superconductivity in Gallium-substituted Ba8Si46 ClathratesYang Li
We report a joint experimental and theoretical investigation of superconductivity in Ga-substituted type-I silicon clathrates. We prepared samples of the general formula Ba8Si46−xGax, with different values of x. We show that Ba8Si40Ga6 is a bulk superconductor, with an onset at TC=3.3 K. For x=10 and higher, no superconductivity was observed down to T=1.8 K. This represents a strong suppression of superconductivity with increasing Ga content, compared to Ba8Si46 with TC=8 K. Suppression of superconductivity can be attributed primarily to a decrease in the density of states at the Fermi level, caused by a reduced integrity of the sp3-hybridized networks as well as the lowering of carrier concentration. These results are corroborated by first-principles calculations, which show that Ga substitution results in a large decrease of the electronic density of states at the Fermi level, which explains the decreased superconducting critical temperature within the BCS framework. To further characterize the superconducting state, we carried out magnetic measurements showing Ba8Si40Ga6 to be a type-II superconductor. The critical magnetic fields were measured to be Hc1=35 Oe and Hc2=8.5 kOe.We deduce the London penetration depth 3700 Å and the coherence length 200 Å. Our estimate of the electron-phonon coupling reveals that Ba8Si40Ga6 is a moderate phonon-mediated BCS superconductor.
Palestra plenária do XII Encontro da SBPMat (Campos do Jordão, setembro/outubro de 2013). Palestrante: Mercouri G Kanatzidis - Northwestern University e Argonne National Laboratory (EUA).
Study Some Parameters of Electrical Discharge in N2 and CO2 Without and With ...IOSRJECE
:We study the breakdown voltage under low pressure for N2, CO2 gases of with a magnetic field to the electrode of iron and aluminum with diameter (8.8cm) cm and distance separation between them is (3cm). by using Passion curve, we measur less effort collapsed, and we notice that less effort is linked to the collapse of a function held cities and when the magnetic field will be reduced to shed breakdown voltage. Since the breakdown voltage for CO2 is greater than breakdown voltage N2. Through curved Passion was calculated (훾) and when to shed the magnetic field will increase in value
Vacancy and Copper-doping Effect on Superconductivity for Clathrate MaterialsYang Li
We present a joint experimental and theoretical study of the superconductivity and electronic structures in type-I Cu-doped silicon clathrates and germanium clathrates. The superconducting critical temperature in Ba8Si46–xCux is shown to decrease strongly with copper content increasing. These results are corroborated by CASTEP approach, first-principles simulations calculated from the density-functional theory with plane waves and pseudopotentials. The simulations show that Cu-doping results in a large decrease of electronic density of states in Fermi level, which can explain the superconducting critical temperature decrease with Cu-doping in the BCS theoretical frame. Further, comparison of Ba8Ge46 and Ba8Si46 within the CASTEP approach shows that the superconductivity is an intrinsic property of the sp3 silicon and germanium clathrates without vacancy in the cage framework. By analysis of the density of states (DOS) and reported experimental results of the Zintl-like Ba8Ge43, a new mechanism of vacancy defect is suggested to explain the absence of superconductivity in Ge clathrates, which is of benefit to eliminating the divarication between theoretical prediction and the experimental observation for superconductivity in Ge clathrates. Keeping an entire Si and Ge cage structure without vacancy is the prerequisite for occurrence of superconductivity in clathrates.
Solid-state electrolytes exhibit good safety and stability, and are promising to replace current organic liquid electrolytes in rechargeable battery applications. In this talk, we will present our efforts at developing scalable first principles techniques to design novel solid-state electrolytes. Using the recently discovered Li10GeP2S12 lithium super ionic conductor as an example, we will discuss how various properties of interest in a solid-state electrolyte can be predicted using first principles calculations. We will show how the application of these first principles techniques has suggested two chemical modifications, Li10SiP2S12 and Li10SnP2S12, that retains the excellent Li+ conductivity of Li10GeP2S12 at a significantly reduced cost. These modifications have recently been synthesized, and the measured Li+ conductivities are in excellent agreement with our first principles predictions. We will conclude with a demonstration of how relatively expensive first principles calculations can be intelligently scaled and combined with topological analysis to be a useful screening tool for novel solid-state electrolytes.
In recent years, there have been great interest in alkali-O2 batteries with extremely high specific energies. Li-O2 batteries offer the greatest theoretical specific energy, but currently suffer from large charging overpotentials and low power densities. Na-O2 offers a somewhat lower theoretical specific energy compared to Li-O2, but still a substantial improvement over today’s lithium-ion batteries. In this talk, we will demonstrate how first principles calculations can provide crucial insight into the workings of alkali-O2 batteries. We will elucidate a facile mechanism for recharging Li2O¬¬2 that is accessible at relatively low overpotentials of ~0.3-0.4V and is likely to be kinetically favored over Li2O2 decomposition. We will also demonstrate that sodium superoxide (NaO2) is predicted to be considerably more stable than sodium peroxide (Na2O2) at the nanoscale. Using first principles calculations, we derive the specific electrochemical conditions to nucleate and retain NaO2 and comment on the importance of considering the nanophase thermodynamics when optimizing an electrochemical system.
Superconductivity in Gallium-substituted Ba8Si46 ClathratesYang Li
We report a joint experimental and theoretical investigation of superconductivity in Ga-substituted type-I silicon clathrates. We prepared samples of the general formula Ba8Si46−xGax, with different values of x. We show that Ba8Si40Ga6 is a bulk superconductor, with an onset at TC=3.3 K. For x=10 and higher, no superconductivity was observed down to T=1.8 K. This represents a strong suppression of superconductivity with increasing Ga content, compared to Ba8Si46 with TC=8 K. Suppression of superconductivity can be attributed primarily to a decrease in the density of states at the Fermi level, caused by a reduced integrity of the sp3-hybridized networks as well as the lowering of carrier concentration. These results are corroborated by first-principles calculations, which show that Ga substitution results in a large decrease of the electronic density of states at the Fermi level, which explains the decreased superconducting critical temperature within the BCS framework. To further characterize the superconducting state, we carried out magnetic measurements showing Ba8Si40Ga6 to be a type-II superconductor. The critical magnetic fields were measured to be Hc1=35 Oe and Hc2=8.5 kOe.We deduce the London penetration depth 3700 Å and the coherence length 200 Å. Our estimate of the electron-phonon coupling reveals that Ba8Si40Ga6 is a moderate phonon-mediated BCS superconductor.
Palestra plenária do XII Encontro da SBPMat (Campos do Jordão, setembro/outubro de 2013). Palestrante: Mercouri G Kanatzidis - Northwestern University e Argonne National Laboratory (EUA).
Study Some Parameters of Electrical Discharge in N2 and CO2 Without and With ...IOSRJECE
:We study the breakdown voltage under low pressure for N2, CO2 gases of with a magnetic field to the electrode of iron and aluminum with diameter (8.8cm) cm and distance separation between them is (3cm). by using Passion curve, we measur less effort collapsed, and we notice that less effort is linked to the collapse of a function held cities and when the magnetic field will be reduced to shed breakdown voltage. Since the breakdown voltage for CO2 is greater than breakdown voltage N2. Through curved Passion was calculated (훾) and when to shed the magnetic field will increase in value
Study of Boron Based Superconductivity and Effect of High Temperature Cuprate...IOSR Journals
This paper illustrates the main normal and Boron superconducting state temperature properties of magnesium diboride, a substance known since early 1950's, but lately graded to be superconductive at a remarkably high critical temperature Tc=40K for a binary synthesis. What makes MgB2 so special? Its high Tc, simple crystal construction, large coherence lengths, high serious current densities and fields, lucidity of surface boundaries to current promises that MgB2 will be a good material for both large scale applications and electronic devices. Throughout the last seven month, MgB2 has been fabricated in various shape, bulk, single crystals, thin films, ribbons and wires. The largest critical current densities >10MA/cm2 and critical fields 40T are achieved for thin films. The anisotropy attribution inferred from upper critical field measurements is still to be resolved, a wide range of values being reported, γ = 1.2 ÷ 9. Also there is no consensus about the existence of a single anisotropic or double energy cavity. One central issue is whether or not MgB2 represents a new class of superconductors, being the tip of an iceberg that waits to be discovered. Until now MgB2 holds the record of the highest Tc among simple binary synthesis. However, the discovery of superconductivity in MgB2 revived the interest in non-oxides and initiated a search for superconductivity in related materials, several synthesis being already announced to become superconductive: TaB2, BeB2.75, C-S composites, and the elemental B under pressure.
Microstructural and Dielectric Characterization of Sr doped Ba(Fe0.5Ta0.5)O3 ...theijes
Solid state reaction method was used to synthesize Ba1-xSrx(Fe0.5Ta0.5)O3 ceramic(x=0, 0.1, 0.2, 0.3, 0.4 and 0.5). The raw materials of making Sr doped Ba(Fe0.5Ta0.5)O3 were BaCO3, SrCO3, Fe2O3, Ta2O5 (purity better than 99%). Pellet and ring shaped samples prepared from each composition were sintered at 1400 and 1450ºC for 5 hour. The phase formation of Ba1-xSrx(Fe0.5Ta0.5)O3 was checked using X-ray diffraction (XRD) technique and observed a cubic perovskite crystal structure in space group Pm3m (221). Microstructure of the individual compound was examined by the field emission scanning electron micrograph (FESEM). Grain size was found to be varied with Sr content. The lattice parameter decreased with increasing Sr content. Dielectric spectroscopy was applied to investigate the electrical properties of BSFT at room temperature and in a frequency range of 100Hz–100 MHz. An analysis of the dielectric constant εʹ and loss tangent tan with frequency was performed assuming a distribution of relaxation times. The low frequency dielectric dispersion corresponds to the DC electrical conductivity.
Study the effect of Mn2+ ions on the ac electrical properties of some iron do...IJRES Journal
Oxide glasses doped with transition metal ions are of high interest because of their variant applications in both science and technology fields. However, the normal melt quench method have used to prepared some iron doped phosphate glasses according the following molecular formula: (65-x) mol% P2O5 - 20 mol% Na2O - 15 mol% Fe2O3 - x mol% MnO, Where x= 0, 5,10, 20, 25. The room temperature Mössbauer Effect ME Spectra used to characterized the glassy state homogeneity of these glasses. ME spectra show, for all glasses, no magnetic field participate which mean good glassy state formation. The ac electrical transport properties were also measured, as function of temperature up to 500k. It was found that the ac conductivity increased with the gradual increase of Mn2+ cations, while the electrical activation energy decreased.
International Journal of Engineering Research and Applications (IJERA) is an open access online peer reviewed international journal that publishes research and review articles in the fields of Computer Science, Neural Networks, Electrical Engineering, Software Engineering, Information Technology, Mechanical Engineering, Chemical Engineering, Plastic Engineering, Food Technology, Textile Engineering, Nano Technology & science, Power Electronics, Electronics & Communication Engineering, Computational mathematics, Image processing, Civil Engineering, Structural Engineering, Environmental Engineering, VLSI Testing & Low Power VLSI Design etc.
Richard's aventures in two entangled wonderlandsRichard Gill
Since the loophole-free Bell experiments of 2020 and the Nobel prizes in physics of 2022, critics of Bell's work have retreated to the fortress of super-determinism. Now, super-determinism is a derogatory word - it just means "determinism". Palmer, Hance and Hossenfelder argue that quantum mechanics and determinism are not incompatible, using a sophisticated mathematical construction based on a subtle thinning of allowed states and measurements in quantum mechanics, such that what is left appears to make Bell's argument fail, without altering the empirical predictions of quantum mechanics. I think however that it is a smoke screen, and the slogan "lost in math" comes to my mind. I will discuss some other recent disproofs of Bell's theorem using the language of causality based on causal graphs. Causal thinking is also central to law and justice. I will mention surprising connections to my work on serial killer nurse cases, in particular the Dutch case of Lucia de Berk and the current UK case of Lucy Letby.
The ability to recreate computational results with minimal effort and actionable metrics provides a solid foundation for scientific research and software development. When people can replicate an analysis at the touch of a button using open-source software, open data, and methods to assess and compare proposals, it significantly eases verification of results, engagement with a diverse range of contributors, and progress. However, we have yet to fully achieve this; there are still many sociotechnical frictions.
Inspired by David Donoho's vision, this talk aims to revisit the three crucial pillars of frictionless reproducibility (data sharing, code sharing, and competitive challenges) with the perspective of deep software variability.
Our observation is that multiple layers — hardware, operating systems, third-party libraries, software versions, input data, compile-time options, and parameters — are subject to variability that exacerbates frictions but is also essential for achieving robust, generalizable results and fostering innovation. I will first review the literature, providing evidence of how the complex variability interactions across these layers affect qualitative and quantitative software properties, thereby complicating the reproduction and replication of scientific studies in various fields.
I will then present some software engineering and AI techniques that can support the strategic exploration of variability spaces. These include the use of abstractions and models (e.g., feature models), sampling strategies (e.g., uniform, random), cost-effective measurements (e.g., incremental build of software configurations), and dimensionality reduction methods (e.g., transfer learning, feature selection, software debloating).
I will finally argue that deep variability is both the problem and solution of frictionless reproducibility, calling the software science community to develop new methods and tools to manage variability and foster reproducibility in software systems.
Exposé invité Journées Nationales du GDR GPL 2024
Seminar of U.V. Spectroscopy by SAMIR PANDASAMIR PANDA
Spectroscopy is a branch of science dealing the study of interaction of electromagnetic radiation with matter.
Ultraviolet-visible spectroscopy refers to absorption spectroscopy or reflect spectroscopy in the UV-VIS spectral region.
Ultraviolet-visible spectroscopy is an analytical method that can measure the amount of light received by the analyte.
The use of Nauplii and metanauplii artemia in aquaculture (brine shrimp).pptxMAGOTI ERNEST
Although Artemia has been known to man for centuries, its use as a food for the culture of larval organisms apparently began only in the 1930s, when several investigators found that it made an excellent food for newly hatched fish larvae (Litvinenko et al., 2023). As aquaculture developed in the 1960s and ‘70s, the use of Artemia also became more widespread, due both to its convenience and to its nutritional value for larval organisms (Arenas-Pardo et al., 2024). The fact that Artemia dormant cysts can be stored for long periods in cans, and then used as an off-the-shelf food requiring only 24 h of incubation makes them the most convenient, least labor-intensive, live food available for aquaculture (Sorgeloos & Roubach, 2021). The nutritional value of Artemia, especially for marine organisms, is not constant, but varies both geographically and temporally. During the last decade, however, both the causes of Artemia nutritional variability and methods to improve poorquality Artemia have been identified (Loufi et al., 2024).
Brine shrimp (Artemia spp.) are used in marine aquaculture worldwide. Annually, more than 2,000 metric tons of dry cysts are used for cultivation of fish, crustacean, and shellfish larva. Brine shrimp are important to aquaculture because newly hatched brine shrimp nauplii (larvae) provide a food source for many fish fry (Mozanzadeh et al., 2021). Culture and harvesting of brine shrimp eggs represents another aspect of the aquaculture industry. Nauplii and metanauplii of Artemia, commonly known as brine shrimp, play a crucial role in aquaculture due to their nutritional value and suitability as live feed for many aquatic species, particularly in larval stages (Sorgeloos & Roubach, 2021).
hematic appreciation test is a psychological assessment tool used to measure an individual's appreciation and understanding of specific themes or topics. This test helps to evaluate an individual's ability to connect different ideas and concepts within a given theme, as well as their overall comprehension and interpretation skills. The results of the test can provide valuable insights into an individual's cognitive abilities, creativity, and critical thinking skills
Observation of Io’s Resurfacing via Plume Deposition Using Ground-based Adapt...Sérgio Sacani
Since volcanic activity was first discovered on Io from Voyager images in 1979, changes
on Io’s surface have been monitored from both spacecraft and ground-based telescopes.
Here, we present the highest spatial resolution images of Io ever obtained from a groundbased telescope. These images, acquired by the SHARK-VIS instrument on the Large
Binocular Telescope, show evidence of a major resurfacing event on Io’s trailing hemisphere. When compared to the most recent spacecraft images, the SHARK-VIS images
show that a plume deposit from a powerful eruption at Pillan Patera has covered part
of the long-lived Pele plume deposit. Although this type of resurfacing event may be common on Io, few have been detected due to the rarity of spacecraft visits and the previously low spatial resolution available from Earth-based telescopes. The SHARK-VIS instrument ushers in a new era of high resolution imaging of Io’s surface using adaptive
optics at visible wavelengths.
ESR spectroscopy in liquid food and beverages.pptxPRIYANKA PATEL
With increasing population, people need to rely on packaged food stuffs. Packaging of food materials requires the preservation of food. There are various methods for the treatment of food to preserve them and irradiation treatment of food is one of them. It is the most common and the most harmless method for the food preservation as it does not alter the necessary micronutrients of food materials. Although irradiated food doesn’t cause any harm to the human health but still the quality assessment of food is required to provide consumers with necessary information about the food. ESR spectroscopy is the most sophisticated way to investigate the quality of the food and the free radicals induced during the processing of the food. ESR spin trapping technique is useful for the detection of highly unstable radicals in the food. The antioxidant capability of liquid food and beverages in mainly performed by spin trapping technique.
Travis Hills' Endeavors in Minnesota: Fostering Environmental and Economic Pr...Travis Hills MN
Travis Hills of Minnesota developed a method to convert waste into high-value dry fertilizer, significantly enriching soil quality. By providing farmers with a valuable resource derived from waste, Travis Hills helps enhance farm profitability while promoting environmental stewardship. Travis Hills' sustainable practices lead to cost savings and increased revenue for farmers by improving resource efficiency and reducing waste.
Deep Behavioral Phenotyping in Systems Neuroscience for Functional Atlasing a...Ana Luísa Pinho
Functional Magnetic Resonance Imaging (fMRI) provides means to characterize brain activations in response to behavior. However, cognitive neuroscience has been limited to group-level effects referring to the performance of specific tasks. To obtain the functional profile of elementary cognitive mechanisms, the combination of brain responses to many tasks is required. Yet, to date, both structural atlases and parcellation-based activations do not fully account for cognitive function and still present several limitations. Further, they do not adapt overall to individual characteristics. In this talk, I will give an account of deep-behavioral phenotyping strategies, namely data-driven methods in large task-fMRI datasets, to optimize functional brain-data collection and improve inference of effects-of-interest related to mental processes. Key to this approach is the employment of fast multi-functional paradigms rich on features that can be well parametrized and, consequently, facilitate the creation of psycho-physiological constructs to be modelled with imaging data. Particular emphasis will be given to music stimuli when studying high-order cognitive mechanisms, due to their ecological nature and quality to enable complex behavior compounded by discrete entities. I will also discuss how deep-behavioral phenotyping and individualized models applied to neuroimaging data can better account for the subject-specific organization of domain-general cognitive systems in the human brain. Finally, the accumulation of functional brain signatures brings the possibility to clarify relationships among tasks and create a univocal link between brain systems and mental functions through: (1) the development of ontologies proposing an organization of cognitive processes; and (2) brain-network taxonomies describing functional specialization. To this end, tools to improve commensurability in cognitive science are necessary, such as public repositories, ontology-based platforms and automated meta-analysis tools. I will thus discuss some brain-atlasing resources currently under development, and their applicability in cognitive as well as clinical neuroscience.
This presentation explores a brief idea about the structural and functional attributes of nucleotides, the structure and function of genetic materials along with the impact of UV rays and pH upon them.
Rotation of transition metal ions under electric fields possible new superconducting electron pairing mechanism
1. Rotation of Transition Metal Ions under Electric Fields: Possible New
Superconducting Electron Pairing Mechanism
Tiege Zhou
(College of Electronic Information and Optical Engineering, Nankai University, 300350 Tianjin, P. R. China)
E-mail address: zhoutg@nankai.edu.cn
Abstract
Electric field effects in iron- and copper-based superconductors were studied by using the
first-principles calculations based on the density functional theory (DFT). The research objects
include iron-based superconductors (KFe2Se2, LaFeAsO, NdFeAsO, and BaFe2As2) and
copper-based superconductors (YBa2Cu3O7, HgBa2Ca2Cu3O8, Tl2Ba2CaCu2O8, and
Bi2Sr2Ca2Cu3O10). To describe the strong correlation effect of 3d-electrons or 4f-electrons, the
GGA+U method was used. Some results were further verified by the HSE method. The densities
of states (DOS) were given. The change of the charge densities under electric fields is presented to
demonstrate the electric field effect. It is found that the electron clouds of Fe ions in iron-based
superconductors, Nd ions in Nd2Fe2As2O2, and Cu ions in copper-based superconductors change
obviously. The pattern of the change is more like a rigid-body rotation than an elastic deformation.
The author proposed that the rotation of the electron clouds of transition metal ions may be a new
medium of superconducting electron pairing. The author’s views about some issues and
suggestions on follow-up studies are also presented.
Keywords: high temperature superconductivity; electric field effect; electron pairing mechanism;
electron cloud rotation
1. Introduction
In 1986, J. G. Bednorz and K. A. Müller discovered that there may be high-temperature
superconductivity (HTS) in La-Ba-Cu-O oxides [1]
, which revealed a new chapter in the research
of superconductivity. In 1987, M. K. Wu et al. [2]
and Z. X. Zhao et al. [3]
synthesized Y-Ba-Cu-O
superconductors, respectively, almost at the same time. The critical temperature (Tc) for
superconductivity reached 90K and achieved a breakthrough above the liquid nitrogen
temperature. In 1988, H. Maeda, Y. Tanaka, M. Fukutumi, and T. Asano. found BiSrCaCuO
superconductors with a Tc above 100K [4]
. In 1988, Z. Z. Sheng et al. synthesized Tl-containing
superconductors [5][6]
. In 1993, HgBa2CuO4+δ, the first member of the Hg series, was synthesized
by S. N. Putilin et al., with a Tc of 94K [ 7 ]
. In 1993, A. Schilling et al. synthesized
2. 2
HgBa2Ca2Cu3O8+δ, raising the Tc above 130K [8]
. The Tc of Hg-1223 can reach 153 K under a high
pressure [9]
. In addition to copper-based superconductors, iron-based superconductors have also
received widespread attention [ 10 ][ 11 ][ 12 ]
. The Tc of PrFeAsO0.89F0.11 reaches 52K [ 13 ]
and
SmFeAsO0.85 55K [14]
. In 2012, Q. K. Xue et al. successfully grow FeSe thin films with one
unit-cell thickness on the surface of SrTiO3 substrates by the MBE method [15]
. The monolayer
FeSe showed a Tc above the liquid nitrogen temperature (77K). In 2014, Q. K. Xue et al. reported
the FeSe monolayer with a Tc over 100K [16]
.
The discovery of copper- and iron-based superconductors has seriously challenged the BCS
theory, because BCS theory predicts that Tc cannot be so high. Traditional electron-phonon
interaction mechanism failed to explain the electron pairing mechanism and other new phenomena
exhibited in copper- and iron-based superconductors. In 1987, P. W. Anderson [17]
has put forward
the famous RVB model for copper-based superconductors. Though many theories [18][19][20]
have
been proposed so far, the electron pairing mechanism is still under intense debate. Anderson [21]
made it clear in 2007 that many theories about high-temperature superconducting electron pairing
mechanism might be in the wrong direction.
The author believes, to explain the electron pairing mechanism in high-temperature
superconductors, we must go back to the traditional electron pairing mechanism. As early as 1950,
H. Fröhlich [22]
proposed that electron-lattice interaction is the source of superconductivity,
supported by the isotope effect [23][24]
. Based on this, the well-known BCS theory [25][26]
was
developed, explaining the traditional superconductivity successfully. The author argues that the
electronic-phonon interaction in BCS theory is closer to a mathematical tool than a simple and
intuitive physical model. The simple and intuitive model is as follows. The electric field of an
electron will distort the ions’ positions. When the electron leaves, the ions will not restore to the
original positions immediately. This results in a positive charge region which will attract another
electron and thus creates an attractive interaction between electrons. Based on the above
consideration, the author believes that a study of the influence of electric fields on coper- and
iron-based superconductors may provide important information about the electron pairing
mechanism. Although many experiments of HTS under electric fields have been conducted
[27][28][29]
, the main purpose is to change the carrier concentration and thus the superconducting
properties. It is related to new superconducting device preparation, no electron pairing mechanism
involved. In the study of the electric field effect of eight typical unconventional superconductors,
the author found, for the first time, the electron cloud of transition metal ions behaves like a
rigid-body rotation. Based on this discovery, the author proposes a possible new superconducting
electron pairing mechanism. This article describes the research methods, results, possible new
superconducting electron pairing mechanism, and the authors' views on several issues about HTS.
3. 3
2. Research objects and calculation methods
The author selected four typical iron-based superconductors (KFe2Se2, LaFeAsO, NdFeAsO
and BaFe2As2) and four typical copper-based superconductors (YBa2Cu3O7, HgBa2Ca2Cu3O8,
Tl2Ba2CaCu2O8 and Bi2Sr2Ca2Cu3O10). It is worth noting that the objects calculated are not strictly
actual superconductors. They are parent materials, and the author makes them closer to the actual
superconductors by changing the stoichiometries or valence electron numbers.
The first-principles calculation based on DFT was used. Most of the calculations were
conducted within the Vienna Ab-initio Simulation Package (VASP) [30] [31]
. The projector
augmented plane wave (PAW) method [32][33]
was used to describe the interaction between the
valence electrons and the ion cores. The generalized gradient approximation (GGA) of
Perdew-Burke-Ernzerhof (PBE) [34]
was used for the exchange correlation potential. To describe
the strong correlation of the 3d or 4f electrons, the GGA+U method is used. For the 3d orbitals of
Fe and Cu,the Ueff values are 4eV[35]
and 6.5eV[36][37]
, respectively. Plane waves were used to
expand the valence electron wave functions. The cutoff energy is set to 400 eV which has been
tested by taking both accuracy and computing cost into account. The valence electron
configurations of the pseudopotentials are taken as 3p6
3d7
4s1
for Fe (with a radius of 2.200 a.u.),
4s2
4p4
for Se, 3s2
3p6
4s1
for K, 5s2
5p6
5d1
6s2
for La, 4s2
4p3
for As, 4f4
5s2
5p6
6s2
for Nd, 5s2
5p6
6s2
for Ba, 5d10
6s2
for Hg, 3s2
3p6
4s2
for Ca, 3p6
3d10
4s1
for Cu (with a radius of 2.000 a.u.), 2s2
2p4
for
O, 4s2
4p6
4d1
5s2
for Y, 5d10
6s2
6p1
for Tl, 5d10
6s2
6p3
for Bi, and 4s2
4p6
5s2
for Sr. For some results,
further calculations with the Heyd, Scuseria, and Ernzerhof (HSE) [38]
hybrid-functional were
performed for cross validation.
Quantum Espresso (QE) simulation package [39]
and norm-conserving pseudopotentials were
employed in the calculation of iron-based superconductors under uniform electric fields. The
valence electron configurations of the pseudopotentials are taken as 3s2
3p6
3d6
4s2
for Fe (with a
radius of 1.909 a.u.), 4s2
4p4
for Se, 3s2
3p6
4s1
for K, 5s2
5p6
5d1
6s2
for La, 4s2
4p3
for As, 3s2
3p6
4s1
for Ba, and 2s2
2p4
for O. Pseudopotentials with less valence electrons (3d6
4s2
for Fe, 4s1
for K,
and 6s2
for Ba) were also used for comparison. The cut-off energy of the plane wave is set to 80
Ry. The exchange-correlation interaction of electrons is escribed by the GGA+U method. Ueff is
6.5 eV for the 3d orbital of Fe. Set occupations = 'fixed' in the input file. In general, occupations =
'fixed' cannot be used for metal. Considering that the calculated objects are not good conductors, it
is acceptable in the calculation of uniform electric fields, but it is difficult to converge to a high
accuracy. In the following, the author will give an explanation.
The results given below without description are obtained with VASP. When the QE software
package is used, the author will point out. First, the geometry of the system is optimized until all
forces on ions are less than 0.01 eV/Å. After optimization, the influence of an electric field on the
4. 4
charge density is calculated. Calculations of iron- and copper-based superconductors were
converged to 10-5
eV and 10-6
, respectively, for the tolerance on the total energy. There are three
ways of applying an electric field to the system. The first is to insert one Li+
ion at an appropriate
position (denoted by Li+
Insertion); the second is to slightly change the position of some atom
(Slight Change); and the third is to apply a uniform electric field (Uniform E-field) with QE
package.
3. Results and discussion
3.1 K2Fe4Se4-2e and K2Fe4Se4
KFeSe superconductors have different stoichiometries, such as K0.8Fe1.6Se2
[40]
and KxFe2Se2
[41]
. The Tc of K0.8Fe1.6Se2 is 31.8K. To access an antiferromagnetic state, the author adopts
K2Fe4Se4 for calculation. Two cases were calculated. One is K2Fe4Se4-2e, with two valence
electrons subtracted, in which the valence of K is +1, Se is -2, and Fe is +2. The other is K2Fe4Se4,
no electron added or subtracted, in which the valence states are rather complicated. If K is +1 and
Se is -2, then Fe is +3/2. The k-point is set to 10×10×4 when using the GGA+U method, and
6×6×2 when using the HSE method. Fig. 1 shows the DOS of K2Fe4Se4-2e, in which the 3d orbital
of the Fe ion (Fe_d) is also presented. It’s an insulator, and the GGA+U method is in very good
agreement with the HSE method except the bandgap. The GGA+U method gives a bandgap of
about 1.3 eV, whereas the HSE method gives a bandgap of about 1.8 eV.
-15 -10 -5 0 5
-10
0
10
spin down
spin up Fe_d
HSE
E (eV)
DOS(arb.unit)
Fe_d total
spin down
spin up
-10
0
10
(b)
(a)total
GGA+U
Fig. 1 DOS of K2Fe4Se4-2e from GGA+U (a) and HSE (b) method
All the three methods were employed to study the influence of electric fields. The fractional
coordinate of the inserted Li+
ion is (0.5, 0.5, 0.62) and it is 2.55 Å away from the nearest
neighbor Fe, 2.73 Å from Se, and 1.5 Å from K. The original position the Se atom to be changed
is (0.5, 0.5, 0.8682) and then revised to (0.5,0.5,0.8602). The position was changed in the (001)
direction by -0.1 Å. When applying the uniform electric field, QE package is used and the k-point
is set to 6×6×2. The uniform electric field is along (111) direction, with a value of 0.00087 Ry a.u..
Set efield_cart(1) = 0.0005 Ry a.u., efield_cart(2) = 0.0005, and efield_cart(3) = 0.0005 in the
5. 5
main input file. The convergence accuracy reaches 3×10-4
Ha. When the k-point is reduced to
3×3×1, the convergence can reach 1×10-5
Ha, and the result is in accordance with that of 6×6×2
k-point.
Fig. 2 displays the crystal structure, spin density map and the charge density difference
(CDD) with and without electric fields. The yellow color represents a positive value or increase of
the charge density, while the blue color negative or decrease. It can be seen from the spin density
map that there is a clear spin distribution on the iron ions and the antiferromagnetic state is present.
For the three ways of exerting influence of electric field, the charge density around Fe ions
changes significantly. There is no similar change around other atoms. The change is more like a
rigid rotation rather than an elastic deformation, because the change is not entirely along the
direction of the electric field. Some areas increase, while some areas decrease. Furthermore, the
pattern of the change is like 3d electron clouds. The isosurface of the CDD is equal to that of the
spin density, indicating the rotation is obvious. The author is sure that the observed results were
not caused by low computational accuracy, from calculations with different accuracies.
Fig. 2 (a) Crystal structure of K2Fe4Se4 with one Li+
ion inserted; (b) Spin density map (GGA+U, iso = 0.02
num_electron/bohr^3); (c) CDD from Li+
Insertion (GGA+U, iso = 0.02); (d) CDD from Li+
Insertion (HSE, iso =
0.02); (e) CDD from Slight Change (GGA+U, iso = 0.02); (f) CDD from Uniform E-field (QE, GGA+U, iso =
0.02). iso represents isosurface.
Table 1 shows the local magnetic moments (LMM) of the Fe ions in K2Fe4Se4-2e. When
there is no electric field, LMM from the GGA+U method is very close to that from the HSE
method, showing the consistency of the two methods. For the results from QE package, LMMs
from the low accuracy and high k-point calculation are consistent with those from the high
accuracy and low k-point calculation, indicating a converge of 3×10-4
Ha is reasonable. The
change of LMMs with and without electric fields is small, which indicates the electric field did not
change the nature of the system significantly.
6. 6
Table 1 LMM (μB) of Fe atoms in K2Fe4Se4-2e
Method Fe1 Fe2 Fe3 Fe4
GGA+U No field 3.384 3.384 -3.384 -3.384
Li+
Insertion 3.453 3.322 -3.599 -3.274
Slight Change 3.388 3.361 -3.385 -3.441
HSE No field 3.376 3.376 -3.376 -3.376
Li+
Insertion 3.481 3.273 -3.507 -3.237
QE(662k) No field 3.229 3.229 -3.193 -3.193
Uniform E-field 3.276 3.301 -3.295 -3.299
QE(331k) No field 3.227 3.227 -3.227 -3.227
Uniform E-field 3.289 3.289 -3.289 -3.289
In addition, increasing or decreasing the lattice constant by 2.5%, the same rotation can be
observed. For Figure 2 (c), increasing the plane wave cutoff energy to 500eV, the results are
consistent with that of 400eV. Calculations with valence electrons as 3d6
4s2
(1.9915 a.u.) for Fe
and 4s1
for K were performed. The k-point is 6×6×2 and the convergence reaches 1×10-6
Ha. The
results are consistent with the previous, showing the observed rotation comes from the 3d
electrons mainly.
For K2Fe4Se4, with no electron subtracted or added, the results show that there is also a
significant rotation of the electron cloud of the Fe ions.
3.2 LaFeAsO
The author calculated (LaFeAsO)2 directly, without increase or decrease of the number of the
valence electrons. For the GGA+U method, the k-point is set to 10×10×6. For the HSE method,
the k-point is set to 6×6×2. Fig. 3 shows the DOS. The two methods give similar DOS for the
d-orbitals of the Fe atoms.
-15 -10 -5 0 5
-5
0
5
totalFe_d
spin down
spin up
HSE
E (eV)
DOS(arb.unit)
Fe_d total
spin down
spin up
-5
0
5
(b)
(a)
GGA+U
Fig. 3 DOS of (LaFeAsO)2 from GGA+U (a) and HSE (b) method
When calculating the influence of electric field, the coordinate of the inserted Li+
ion is (0.58,
7. 7
0.58, 0.62). The Li+
ion is 1.877Å, 1.979Å, and 2.407Å from the nearest neighbor Fe atom, As
atom, and La atom, respectively. The original coordinate of the As atom to be changed is (0.75,
0.75, 0.3363), and then revised to (0.75, 0.75, 0.3113). The position was changed in the (001)
direction by -0.22 Å. When using the QE package, the k-point is set to 6×6×2. The convergence
reaches 1×10-5
Ha. Fig. 4 shows the crystal structure, CDDs and the total charge density (3d6
4s2
are taken as valence electrons for Fe).
Fig. 4 (a) Crystal structure of (LaFeAsO)2 with one Li+
ion inserted; (b) CDD from Li+
Insertion (GGA+U, iso =
0.02); (c) CDD from Li+
insertion (HSE, iso = 0.02); (d) Total charge density (GGA+U, iso = 0.3 ); (e) CDD
from Slight Change (HSE, iso = 0.02); (f) CDD from Uniform E-field (QE, iso = 0.02)
It can be seen from all the CDDs that there is a significant rotation of the electron clouds of
the Fe ions. From Fig. 4(d), the distribution of the charge density around the iron atom does not
have a perfect spherical symmetry. The author believes that this is the main reason for the rotation
under electric fields.
LMMs are given in Table 2. The results given by different methods are consistent, and the
applied electric field has little effect on the local magnetic moments.
Table 2 LMM of Fe in (LaFeAsO)2
Method Fe1 Fe2
GGA+U No field 3.261 -3.261
Li+
Insertion 3.286 -3.287
Slight Change 3.280 -3.332
HSE No field 3.282 -3.282
Li+
Insertion 3.244 -3.244
Slight Change 3.349 -3.360
QE No field 3.232 -3.222
Uniform E-field 3.219 -3.230
8. 8
The calculation with 3d6
4s2
as valence electrons for Fe shows that there is a significant
rotation of the electron cloud. Increasing the cut off energy of the plane wave to 500 eV gives the
same results as 400 eV. The author also observed obvious rotation when 0.2 electrons added.
In addition, the author calculated a 6×2×1 supercell. The position of the inserted Li+
ion is
(0.79, 0.38, 0.58); the coordinate of the As atom to be changed was (0.2083, 0.6250, 0.6637) and
decreased by 0.01 (0.082 Å) in the y direction. Fig. 5 shows the CDDs. The most important
discovery is significant rotation occurs far away from the position where the electric field is
applied. This shows that electron clouds of Fe ions in iron-based superconductors are more
sensitive to the electric field, which is different from that of copper-based superconductors given
below. The electron clouds of some Fe ions change obviously, but some not, which may be caused
by the interaction between the charge density changes of different Fe ions.
Fig. 5 CDD of the 6×2 supercell from Li+
Insertion (GGA+U, iso = 0.01) (a) and Slight Change (GGA+U, iso =
0.01) (b)
3.3 Nd2Fe2As2O2
For the investigation of Nd2Fe2As2O2, the k-point is set to 10×10×5. Since Nd is a 4f
transition metal atom, it has strong spin-orbital coupling and strong correlation. The spin-orbital
coupling effect is considered in the calculation and the strong correlation effect is described by the
GGA+U method (Ueff = 7.0 eV). The calculation of uniform electric field together with
spin-orbital coupling may be too expensive, so the author gives only the result of inserting one Li+
ion.
The Li+
ion is located at (0.5, 0.25, 0.317), which is 1.912 Å, 1.927 Å, and 2.281 Å from the
nearest Nd, Fe, and As, respectively. The author also gives the results when the Li+
ion is closer to
one Nd atom. The coordinate of the Li+
ion is (0.4, 0.4, 0.2) and it is 1.54 Å from the nearest Nd
atom. Fig. 6 shows the CDDs. When the distance between the Li+
ion and the Nd atom is large,
rotation of the electron cloud of the Nd ion cannot be observed. When the distance decreased,
obvious change appears. This suggests that the 4f electron cloud of Nd may also play an important
role in superconductivity.
9. 9
Fig. 6 CDDs from Li+
Insertion (GGA+U, iso = 0.02). Li+
ion is 1.912 Å (a) and 1.54 Å (b) from the nearest Nd
atom, respectively.
3.4 Ba1-xKxFe2As2
The Tc of Ba1-xKxFe2As2 can reach 38K [42]
. Ba2Fe4As4 and BaKFe4As4 were employed in the
calculation, corresponding to x = 0 and 0.5, respectively. For the valence state of Ba2Fe4As4, As is
-3, Ba is +2, and Fe is +2. For BaKFe4As4, As is -3, Ba is +2, K is +1 and Fe is +9/4. The k-point
is set to 10×10×4 when using the GGA+U method and 6×6×2 when using the HSE method. Fig. 7
shows the DOS of Ba2Fe4As4. The two methods are in good agreement, except that the GGA+U
method gives a lower bandgap.
-15 -10 -5 0 5
-10
0
10
totalFe_d
spin down
spin up
HSE
E (eV)
DOS(arb.unit)
Fe_d total
spin down
spin up
-10
0
10
(b)
(a)
GGA+U
Fig. 7 DOS of Ba2Fe4As4 from GGA+U (a) and HSE (b) method
Two methods were used to calculate the electric field effect. One is to insert one Li+
ion. The
coordinate is (0.5,0.5,0.69), and it is 2.470 Å, 2.191 Å, and 2.268 Å away from the nearest
neighbor Ba, As, and Fe, respectively. The other is to apply a uniform electric field by the QE
package, in which k-point is set to 6×6×2. The value and direction of the electric field are the same
as those given above. The convergence reaches 1×10-4
Ha. Fig. 8 shows the crystal structure and
the results, in which the CDD of BaKAs4Fe4 from Li+
Insertion is also given. The rotation of the
charge densities of Fe ions is obvious.
10. 10
Fig. 8 (a) Crystal structure of Ba2Fe4As4; (b) CDD of Ba2Fe4As4 from Li+
Insertion (GGA+U, iso = 0.02); (c) CDD
of Ba2Fe4As4 from Uniform E-field (QE, GGA+U, iso = 0.02); (d) CDD of BaKAs4Fe4 from Li+
Insertion
(GGA+U, iso = 0.02)
For BaKAs4Fe4, apparent charge density rotation can also be observed when the position of
an As atom is slightly changed or an uniform electric field is applied
3.5 (YBa2Cu3O7)2
To access an antiferromagnetic state, (YBa2Cu3O7)2 was used, no electron added or
subtracted. When the GGA+U method is adopted, the k-point is set to 8×8×4. When the HSE
method is used, the k-point is 4×4×2. Fig. 9 shows the DOS.
-15 -10 -5 0 5
-20
-10
0
10
20
3*Cu_d
total
spin down
spin up
HSE
DOS(arb.unit)
E (eV)
3*Cu_d
total
spin down
spin up
-20
-10
0
10
20
(b)
(a)
GGA+U
Fig. 9 DOS of (YBa2Cu3O7)2 from GGA+U (a) and HSE (b) method. Cu_d has been multiplied by 3 for clarity.
The spin density of the system was calculated. The effect of an electric field induced by a
slight change in the position of one oxygen atom in the copper oxide plane was calculated. The
original coordinate of the oxygen atom was (0.75, 0.25, 0.62245), and then changed to (0.8, 0.3,
0.62245). The position was changed in the (110) direction by 0.39 Å. The method is GGA+U, and
the result was validated by HSE. The author also performed the calculation for the vertical change
(0.23 Å) of the oxygen atom. Substituting Cu with Zn was also calculated with the GGA+U
method (3d electrons of Zn are regarded as valence electrons and set Ueff = 6.5eV), and the
position of oxygen atom was changed along (110). Fig. 10 shows the crystal structure and results.
11. 11
Fig. 10 (a) Crystal structure; (b) Spin density map (GGA+U, iso = 0.01); (c) CDD form Slight Change (GGA+U,
iso = 0.004); (d) CDD from Slight Change (HSE, iso = 0.004); (e) CDD from Slight Change along z direction
(GGA+U, iso = 0.004); (f) CDD of YBaZnO from Slight Change (GGA+U, Ueff = 6.5eV, iso = 0.004)
It can be seen from the spin density map that the Cu ions in the copper-oxygen layer exhibit
an antiferromagnetic state. The electron cloud of Cu ions shows an obvious rotation. It is worth
noting that the isourface is about one order of magnitude smaller than that of Fe ions in iron-based
superconductors. The electron cloud of Zn did not rotate at all. Calculations with Ueff = 0 show
that the electron cloud of Zn does not rotate too. Table 3 gives the LMM of the Cu atom. When the
electric field is not applied, the results given by the GGA+U and the HSE method are very
consistent. When there is an influence, the change of the LMM is very small.
Table 3 LMM of the Cu atom in (YBa2Cu3O7)2
Method Cu
GGA+U No field 0.634
Slight Change xy 0.631
Slight Change z 0.641
HSE No field 0.631
The rotation is also observed in (YBa2Cu3O7)2 with 0.3 or 2 electrons added. The author
believes that, if the 3d orbitals of Cu is not fully filled, the electron will rotate under electric fields.
When the 3d shell is filled, the rotation cannot be observed.
3.6 (HgBa2Ca2Cu3O8)2
To achieve an antiferromagnetic state, (HgBa2Ca2Cu3O8)2 was used. No electrons were added
or subtracted. With the GGA+U method, the k-point is set to 8×8×4. With the HSE method, the
k-point is set to 4×4×2. Fig. 11 shows the DOS. The 3d orbital of Cu (Cu_d) is of the middle
copper-oxide layer.
12. 12
-15 -10 -5 0 5
-20
-10
0
10
20
total
3*Cu_dspin down
spin up (a)
(b)
HSE
DOS(arb.unit)
E (eV)
3*Cu_d
total
spin down
spin up
-20
-10
0
10
20
GGA+U
Fig. 11 DOS of (HgBa2Ca2Cu3O8)2 from GGA+U (a) and HSE (b) method.
The effect of electric fields is calculated by slightly changing one oxygen atom in the middle
copper-oxygen layer. The original position of the oxygen atom is (0.75, 0.25, 0.5) and then
changed to (0.8, 0.3, 0.5). The position was changed in the (110) direction by 0.39 Å. The result
was verified by the HSE method. Fig. 12 shows the crystal structure, spin density map and CDDs
with and without electric fields. The charge density of Cu ions exhibits clear rotations and the
GGA+U method gives consistent result with the HSE method.
Fig. 12 (a) Crystal structure; (b) Spin density map (HSE, iso = 0.01); (c) CDD from Slight Change (GGA+U, iso =
0.003); (d) CDD from Slight Change (HSE, iso = 0.003)
Table 4 gives the LMM. Consistency between the HSE and GGA+U method can be seen and
the effect of a Slight Change on the LMM is very small.
Table 4 LMM of the Cu atom in (HgBa2Ca2Cu3O8)2
Method Cu
GGA+U No field 0.603
Slight Change 0.600
HSE No field 0.618
Slight Change 0.619
13. 13
Calculations of (HgBa2Ca2Cu3O9)2/(HgBa2Ca2Cu3O9+2e)2 show that there are significant
rotations of the electron cloud of copper atoms.
Further, a 4×1×1 supercell of (HgBa2Ca2Cu3O8)2 was calculated. The original coordinate of
the oxygen atom to be changed is (0.1875, 0.25, 0.5), and then changed to (0.2, 0.3, 0.5). The
CDD is displayed in Fig. 13. There is a clear rotation on Cu atom. However, no rotation occurs far
away from where the influence is applied. This is totally different from that of iron-based
superconductors. For iron-based superconductors, rotation can be observed further away.
Fig. 13 CDD of the 4×1×1 supercell from Slight Change (GGA+U, iso = 0.003)
3.7 (Tl2Ba2CaCu2O8)4
To access an antiferromagnetic state, the author adopted (Tl2Ba2CaCu2O8)4, no electron added
or subtracted. The GGA+U method is used, and the k-point is set to 6×6×1. Fig. 14 shows the
DOS.
-15 -10 -5 0 5
-40
-20
0
20
40
GGA+U
DOS(arb.unit)
E (eV)
4*Cu_d
total
spin down
spin up
Fig. 14 DOS of (Tl2Ba2CaCu2O8)4 from GGA+U method
The position of the O atom was changed by 0.39 Å, -0.39 Å and 0.78 Å, respectively, in the
(110) direction. Fig. 15 displays the CDDs. It can be clearly seen that the electron cloud of the
Cu2+
ion rotates with the change of the O atom’s position. Slightly changing the position of
oxygen atoms near Tl or Ba, the author did not observe the rotation of the electron cloud of Tl or
Ba.
Fig. 15 (a) Copper-oxygen layer; (b) CDD from Slight Change of 0.39Å; (c) CDD from Slight Change of -0.39 Å;
14. 14
(c) CDD from Slight Change of 0.78Å (GGA+U, iso = 0.003)
3.8 (Bi2Sr2Ca2Cu3O10)4
(Bi2Sr2Ca2Cu3O10)4 was adopted, no electron added or subtracted. The k-point is set to 5×5×1.
Fig. 16 shows the DOS.
-15 -10 -5 0 5
-40
-20
0
20
40
GGA+U
DOS(arb.unit)
E (eV)
6*Cu_d
total
spin down
spin up
Fig. 16 DOS of (Bi2Sr2Ca2Cu3O10)4 from GGA+U method
The system has three adjacent copper-oxygen layers, the position of one oxygen atom in the
uppermost copper-oxygen layer is changed. The original coordinate is (0.75, 0.25, 0.586189), and
then changed to (0.8, 0.3, 0.586189). The author also studied the case of increasing or decreasing
the lattice constant. Fig. 17 shows the results. There is also a significant rotation of the electron
cloud of Cu ions when the lattice constant is increased or decreased.
Fig. 17 (a) CDD from Slight Change (GGA+U, iso = 0.002), (b) The lattice constant decreases by 2.5%; (c) The
lattice constant increases by 2.5%
It can be seen from the results of the above eight systems all the electron clouds of Cu ions or
Fe ions have obvious changes under electric fields.The author believes this change should be
called a rotation not an elastic deformation, because the CDD does not simply follow the direction
of the electric field, but increases in some areas and decreases in others.
Is this rotation just of 3d (or 4f) electron cloud? Considering the orthogonality of the atomic
orbitals, the author thinks a change of the outer electron clouds will inevitably affect the inner
electron clouds. So, the inner electron cloud will rotate too. However, the rotation of the inner
electron cloud is difficult to observe because they have spherical symmetry.
Why do electron clouds rotate? We know that transition metal ions (3d or 4f) have
incompletely filled 3d or 4f orbitals. The electron cloud does not have perfect spherical symmetry.
15. 15
It is like a polar molecule and will rotate under electric fields.
In addition to the above eight typical unconventional superconductors, other superconductors,
such as metallic Nb, heavy fermion superconductor UPt3, rare earth superconductor SmRh4B4, et
al., have incompletely filled 3d or 4f shells. They are likely to rotate under an electric field and
thus play an important role in superconducting electron pairing.
4. Possible Superconducting Electron Pairing Mechanism, Views on some issues, and
Research Prospect
4.1 Mechanism
Mr. Anderson has raised the issue of whether a glue exists in high temperature
superconductors. The author believes it does exist. Combined with the simple and intuitive model
of electron-phonon interaction and the fact that transition-metal ions’ electron clouds rotate under
an electric field, the author proposes that the rotation of the transition metal electron cloud is the
glue. When an electron comes to a new location, the electron cloud of the transition metal ions in
the vicinity will rotate. In this way, the charge density around the electron will decrease
(equivalent to the emergence of a positive charge). When the electron leaves, the electron cloud of
the transition metal ions will not relax immediately (it is so crucial that that the author will discuss
it later), so that there will be a region lack of charge (equivalent to a positive charge region) that
will attract another electron. Attraction between electrons appears. This mechanism is essentially
the same as the electron-phonon interaction, except that the medium is the rotation of the electron
cloud, not the displacement of ions.
4.2 Author’s views on some issues
4.2.1 Relaxation time of the electron cloud rotation
The most important point in the new pairing mechanism is the relaxation time of the electron
cloud's rotation. If the relaxation time is smaller than that of the elastic deformation of the electron
cloud, then it cannot be the glue. The author believes that this relaxation time will not be so small,
because the inner electrons will also rotate due to the requirement of orthogonality of electron
wavefunctions. This is the most important follow-up study.
4.2.2 Is the rotation of electron clouds of ions or ions?
The author think ‘Rotation of ions’ is better,because it is more simple and intuitive.
4.2.3 The role of strong correlation
For the electron cloud rotation, iron-based superconductors are more obvious than
copper-based superconductors, but the Tc of copper-based superconductors is higher than that of
iron-based superconductors. In addition to different electronic structures, the author believes that
the strong correlation plays an important role. Copper-based superconductors have stronger
16. 16
correlation effect than iron-based superconductors. The screening is strong in iron-based
superconductors, which causes a lower Tc. For the relationship between strong correlation and
high Tc, the author believes strong correlation is a necessary but not sufficient condition for high
Tc. In strongly correlated systems, electrons cannot be described by free electrons or weakly
interacting quasi-particles, so that a strong attraction is possible. The screening in traditional
superconductors is strong, on the one hand reducing the repulsion between electrons, but also lead
to a weak attraction.
4.2.4 Relationship between magnetism and unconventional superconductivity
The author thinks that the rotation of the electron cloud of transition metal ions is the
fundamental reason for the unconventional superconductivity. The rotation is because the atomic
shells are not fully filled and no spherical symmetry present. When there is an electric field, it will
rotate. Magnetism is also because the shells are not fully filled.
4.3 Research prospect
4.3.1 The research in this article is mainly concentrated on the existence of the electron cloud
rotation. More detailed researches are needed. For example, the projected DOS and more analysis
should be given. In addition, the study also need more accurate calculations, such as the use of the
Quantum Monte Carlo method. Most results of this paper are qualitative. Further research requires
quantitative analysis, such as quantification of the applied electric field and quantification of the
electron cloud rotation.
4.3.2 The author believes that determination of the relaxation time of the electron cloud rotation is
crucial. Theoretical and experimental studies of the electron cloud rotation and the relaxation time
should be given.
4.4.3 New theories and application. For example, theory of the interaction between electrons and
the rotation of ions, possible long-range modes of the rotation in iron-based superconductors, and
influence (or application) of rotation of transition metal ions in other fields.
4. Conclusion
The author studied eight typical unconventional superconductors. The electron cloud of
transition metal ions is found to rotate under electric fields. Extensive calculations show that if
there is an incompletely filled electronic orbital, the electron cloud will rotate. If the orbital is
filled, the electron cloud will not rotate. The authors believe that the rotation of transition metal
ion’s electron cloud may be a new medium of superconducting electron pairing, just as lattice
deformation is the conventional superconducting electron pairing medium. The author’ views on
this new possible pairing mechanism, strong correlation and superconductivity, magnetism and
superconductivity, and follow up studies are given.
17. 17
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