Independent Electron Research Articles

Physics-Inspired Evolutionary Machine Learning Method: From the Schrödinger Equation to an Orbital-Free-DFT Kinetic Energy Functional.

We introduce a machine learning (ML)-supervised model function (which is in fact a functional rather than a regular function) that is inspired by the variational principle of physics. This ML hypothesis evolutionary method, termed ML-Ω, allows us to go from data to differential equation(s) underlying the physical (chemical, engineering, etc.) phenomena from which the data are derived from. The fundamental equations of physics can be derived from this ML-Ω evolutionary method when the proper training data is used. By training the ML-Ω model function with only three hydrogen-like atom energies, the method can find Schrödinger's exact functional and, from it, Schrödinger's fundamental equation. Then, in the field of density functional theory (DFT), when the model function is trained with the energies from the known Thomas-Fermi (TF) formula , it correctly finds the exact TF functional. Finally, the method is applied to find a local orbital-free (OF) functional expression of the independent electron kinetic energy functional Ts based on the γTFλvW model. By considering the theoretical energies of only five atoms (He, Be, Ne, Mg, and Ar) as the training set, the evolutionary ML-Ω method finds an ML-Ω-OF-DFT local Ts functional (γTFλvW(0.964,1/4)) that outperforms all the OF-DFT functionals of a representative group. Moreover, our ML-Ω-OF functional overcomes the difficulty of LDA's and some local generalized gradient approximation (GGA)-DFT's functionals to describe the stretched bond region at the correct spin configuration of diatomic molecules. Nonsmooth and nonclosed form functionals can be considered in the ML-Ω model function and still be effectively trained. Although our evolutionary ML-Ω model function can work without an explicit prior-form functional, by using the techniques of symbolic regression, in this work, we exploit prior-form functional expressions to make the training process simpler and faster. The ML-Ω method can be considered at the intersection of ML and the natural sciences.

Breaking the scaling relations of effective CO2 electrochemical reduction in diatomic catalysts by adjusting the flow direction of intermediate structures.

The electrocatalytic carbon dioxide reduction reaction (CO2RR) is a promising approach to achieving a sustainable carbon cycle. Recently, diatomic catalysts (DACs) have demonstrated advantages in the CO2RR due to their complex and flexible active sites. However, our understanding of how DACs break the scaling relationship remains insufficient. Here, we investigate the CO2RR of 465 kinds of graphene-based DACs (M1M2-N6@Gra) formed from 30 metal atoms through high-throughput density functional theory (DFT) calculations. We find that the intermediates *COOH, *CO, and *CHO have multiple adsorption states, with 11 structural flow directions from *CO to *CHO. Four of these structural flow directions have catalysts that can break the linear scale relationship. Based on the adsorption energy relationship between *COOH, *CHO and *CO, we propose the concepts of linear scaling, moderate breaking, and severe deviation regions, leading to the establishment of new descriptors that identify 14 catalysts with potential superior performance. Among them, ZnRu-N6@Gra and CrNi-N6@Gra can reduce CO2 to CH4 at a low limiting potential. We also discovered that DACs have independent bidirectional electron transfer channels during the adsorption and activation of CO2, which can significantly improve the flexibility and efficiency of regulating the electronic structure. Furthermore, through machine learning (ML) analysis, we identify electronegativity, atomic number, and d electron count as key determinants of catalyst stability. This work provides new insights into the understanding of the DAC catalytic mechanism, as well as the design and screening of catalysts.

Influence of the external magnetic field on structural characteristics of granular Co-Cu thin film alloys

We present the results of experimental studies of the influence of an external magnetic field on the structural characteristics (surface roughness and structural entropy) of nanogranular thin-film system based on Co and Cu. The samples CoxCu100-x in a wide range of compositions (17 at. % ≤ x ≤ 69 at. %) with the thickness of d = 35 nm were obtained by electron-beam co-evaporation using two independent electron guns. After obtaining, the films were annealed in a vacuum at a temperature of 800 K for 30 min. The studies of magnetoresistive properties have shown that the maximum giant magnetoresistance (GMR) amplitude (1.7 % in the transverse and 1.6 % in the longitudinal measurement geometries) in a magnetic field of H = 4.5 kOe at room temperature was observed in the Co21Cu79 film alloy. Transmission electron microscopy showed that this sample contains hcp-Co granules with a size of L = 5 ÷ 12 nm in a matrix of metastable fcc-Cu(Co) solid solution. The influence of the external magnetic field on the structural characteristics and surface morphology of the Co21Cu79 thin-film alloy was investigated using atomic force microscopy (AFM). It was found that a first impact of application of external magnetic field with H = 0.5 kOe causes a decrease in the values of the arithmetic mean Ra, and quadratic mean Rq, of the film roughness and structural entropy S. A decreases in Ra by 8.5 %, Rq by 6.5 %, and structural entropy S by 6.5 % were observed. After application of a larger magnetic field with H = 1.0 kOe and during the subsequent relaxation of the structure within 15 h after the field is turned off, the values of the structural parameters of the film surface did not change significantly.

Nanoplastics in Water: Artificial Intelligence-Assisted 4D Physicochemical Characterization and Rapid In Situ Detection.

For the first time, we present a much-needed technology for the in situ and real-time detection of nanoplastics in aquatic systems. We show an artificial intelligence-assisted nanodigital in-line holographic microscopy (AI-assisted nano-DIHM) that automatically classifies nano- and microplastics simultaneously from nonplastic particles within milliseconds in stationary and dynamic natural waters, without sample preparation. AI-assisted nano-DIHM identifies 2 and 1% of waterborne particles as nano/microplastics in Lake Ontario and the Saint Lawrence River, respectively. Nano-DIHM provides physicochemical properties of single particles or clusters of nano/microplastics, including size, shape, optical phase, perimeter, surface area, roughness, and edge gradient. It distinguishes nano/microplastics from mixtures of organics, inorganics, biological particles, and coated heterogeneous clusters. This technology allows 4D tracking and 3D structural and spatial study of waterborne nano/microplastics. Independent transmission electron microscopy, mass spectrometry, and nanoparticle tracking analysis validates nano-DIHM data. Complementary modeling demonstrates nano- and microplastics have significantly distinct distribution patterns in water, which affect their transport and fate, rendering nano-DIHM a powerful tool for accurate nano/microplastic life-cycle analysis and hotspot remediation.

Polarized Ultrathin BN Induced Dynamic Electron Interactions for Enhancing Acidic Oxygen Evolution

AbstractDeveloping ruthenium‐based heterogeneous catalysts with an efficient and stable interface is essential for enhanced acidic oxygen evolution reaction (OER). Herein, we report a defect‐rich ultrathin boron nitride nanosheet support with relatively independent electron donor and acceptor sites, which serves as an electron reservoir and receiving station for RuO2, realizing the rapid supply and reception of electrons. Through precisely controlling the reaction interface, a low OER overpotential of only 180 mV (at 10 mA cm−2) and long‐term operational stability (350 h) are achieved, suggesting potential practical applications. In situ characterization and theoretical calculations have validated the existence of a localized electronic recycling between RuO2 and ultrathin BN nanosheets (BNNS). The electron‐rich Ru sites accelerate the adsorption of water molecules and the dissociation of intermediates, while the interconnection between the O‐terminal and B‐terminal edge establishes electronic back‐donation, effectively suppressing the over‐oxidation of lattice oxygen. This study provides a new perspective for constructing a stable and highly active catalytic interface.

Polarized Ultrathin BN Induced Dynamic Electron Interactions for Enhancing Acidic Oxygen Evolution.

Developing ruthenium-based heterogeneous catalysts with an efficient and stable interface is essential for enhanced acidic oxygen evolution reaction (OER). Herein, we report a defect-rich ultrathin boron nitride nanosheet support with relatively independent electron donor and acceptor sites, which serves as an electron reservoir and receiving station for RuO2, realizing the rapid supply and reception of electrons. Through precisely controlling the reaction interface, a low OER overpotential of only 180 mV (at 10 mA cm-2) and long-term operational stability (350 h) are achieved, suggesting potential practical applications. In situ characterization and theoretical calculations have validated the existence of a localized electronic recycling between RuO2 and ultrathin BN nanosheets (BNNS). The electron-rich Ru sites accelerate the adsorption of water molecules and the dissociation of intermediates, while the interconnection between the O-terminal and B-terminal edge establishes electronic back-donation, effectively suppressing the over-oxidation of lattice oxygen. This study provides a new perspective for constructing a stable and highly active catalytic interface.

Classical-trajectory model for ionizing proton-ammonia molecule collisions: the role of multiple ionization

We use an independent electron model with semi-classical approximation to electron dynamics to investigate differential cross sections for electron emission in fast collisions of protons with ammonia molecules. An effective potential model for the electronic orbitals is introduced, and utilized in the context of the classical-trajectory Monte Carlo (CTMC) approach for single-electron dynamics. Cross sections differential in electron emission angle and energy are compared with experimental data. Compared to previous scattering-theory based quantum-mechanical results the time-dependent semi-classical CTMC approach provides results of similar quality for intermediate and high ionized electron energies. We find some discrepancies in the total cross sections for q-fold ionization between the present model and independent-atom-model calculations. The double ionization cross sections are considerably larger than recent experimental data which are derived from coincidence counting of charged fragments. The calculated triple ionization cross sections exceed the experimental coincidence data for q = 3 by several orders of magnitude at intermediate energies.

Exploring tunneling ESEEM beyond methyl groups in nitroxides at low temperatures.

Tunneling of methyl rotors coupled to an electron spin causes magnetic field independent electron spin echo envelope modulation (ESEEM) at low temperatures. For nitroxides containing alkyl substituents, we observe this effect as a contribution at the beginning of the Hahn echo decay signal occurring on a faster time scale than the matrix-induced decoherence. The tunneling ESEEM contribution includes information on the local environment of the methyl rotors, which manifests as a distribution of rotation barriers P(V3) when measuring the paramagnetic species in a glassy matrix. Here, we investigate the differences in tunneling behaviour of geminal methyl and ethyl group rotors in nitroxides while exploring different levels of theory in our previously introduced methyl quantum rotor (MQR) model. Moreover, we extend the MQR model to analyze the tunneling ESEEM originating from two different rotor types coupled to the same electron spin. We find that ethyl groups in nitroxides give rise to stronger tunneling ESEEM contributions than methyl groups because the difference between hyperfine couplings of their methyl protons better matches the tunneling frequency. The methyl rotors of both ethyl and propyl groups exhibit distributions at lower rotation barriers compared to geminal methyl groups. This is in good agreement with density functional theory (DFT) calculations of their rotation barriers and showcases that conformational flexibility impacts the hindrance of rotation. Using Monte-Carlo based fitting in combination with an identifiability analysis of the MQR model parameter space, we extract rotation barrier distributions for the individual rotor types in mixed-rotor nitroxides as well as identify which rotors dominate the observed tunneling contribution in the Hahn echo decay signal.

Ultrahigh thermoelectric power factor achieved in Yb filled CoSb3 skutterudites through additional Al doping

Cage-like CoSb3 skutterudites has received widespread attentions due to its low cost, moderate band gap and nearly independent electron–phonon regulation. Unfortunately, recent researches revealed that external fillers occupying the icosahedral voids of Co-Sb framework might cause localized lattice distortion and strain which put extra difficulty for charge carrier transport. Here, we took use of additional Al atoms with smaller atomic radii to substitute Sb atoms in Yb single filled CoSb3 for the purpose of alleviating the local strain cause by Yb filling. It was found that trace amount of additional Al doping can significantly improve the carrier mobility from 33.9 cm2V1s−1 for Yb0.25Co4Sb12 to 49.8 cm2V-1s−1 for Al0.03Yb0.25Co4Sb12, resulting in an ultrahigh power factor of 72.0 μWcm-1K−2 at 873 K in the later sample. Our findings might shed light on future studies on optimizing the thermoelectric performance of CoSb3-based skutterudites and other material systems.

Quasiparticle approach to collective quantum dielectric response

In current research, we use a generalized quantum multistream model to develop an effective quasiparticle theory for quantum many-body effects. The N-electron Schrödinger–Poisson stream model is reduced to a system of coupled differential equations with new wavefunction representation for collective quantum excitations in the many electron system. The current theory is then applied to the collective quantum statistical behavior of homogenous electron gas. Moreover, the generalized energy dispersion relation, which incorporates the quasiparticle band structure, is used to calculate the linear dielectric response of collective quantum excitations in the electron gas with arbitrary degree of degeneracy beyond many-body theories, limiting assumptions such as the independent electron and the random phase approximations. Important parameters of electron gas such as the dynamic structure factor, the loss function, the static charge screening, optical reflectivity, and the electronic stopping power are investigated as applications of current theory. The quasiparticle theory incorporates effects both due to single-electron excitations as well as the electrostatic interaction among electrons in a single picture. Existence of Van-Hove-like singularity at the plasmon wavenumber leads to distinct features of quasiparticle response to electromagnetic perturbations in the electron gas. It is shown that collective quantum excitations in high density electron gas below a given critical electron temperature are blocked due to existence of a large quasiparticle energy bandgap above the Fermi level. A new equation of states is given for the quasiparticle excitation in the electron gas, based on the transition probability of electrons to the quasiparticle level. It is found that, the screening potential of a static charge in quasiparticle model has an oscillatory Lennard–Jones-type attractive form.

Ionization and electron capture in O6+ + He collisions at 0.86, 1.5, 1.94 a.u. velocities

Using the projectile-ion-recoil-ion coincidence method, relative cross sections for single-electron capture, single ionization, double-electron capture, transfer ionization and double ionization in collisions of multiply charged O6+ ions with helium atoms have been measured at 0.86, 1.5, 1.94 a.u. velocities. Calculations based on the semi-classical over-barrier model in the framework of independent electron approximation is employed to discuss various competing reaction mechanisms. These results are also compared with other experimental and theoretical results available in the velocity range considered.

Influence of Lewis acids on the symmetric SN2 reaction

This paper presents a theoretical analysis the effect of non-covalent interactions (NCI) in three different SN2 reactions (X–:CH3X → XCH3:X–, X = Cl, Br and I) has been theoretically analysed in the pre-reactive complexes, TS and products. A total of eighteen Lewis acids (LAs: FH, ClH, FCl, I2, SeHF, SeF2, PH2F, PF3, SiH3F, SiF4, BH3, BF3, BeH2, BeF2, LiH, LiF, Au2 and AgCl) interact with the halogen atom of the CH3X molecule. To analyse the strength of the non-covalent interactions, both the independent gradient model tool and electron density maps have been employed. The results reveal that in all cases, the interaction between the anion and the Lewis acid leads to an increase in the transition barriers compared to the parental reaction.

Assessing Mixed Quantum-Classical Molecular Dynamics Methods for Nonadiabatic Dynamics of Molecules on Metal Surfaces.

Mixed quantum-classical (MQC) methods for simulating the dynamics of molecules at metal surfaces have the potential to accurately and efficiently provide mechanistic insight into reactive processes. Here, we introduce simple two-dimensional models for the scattering of diatomic molecules at metal surfaces based on recently published electronic structure data. We apply several MQC methods to investigate their ability to capture how nonadiabatic effects influence molecule-metal energy transfer during the scattering process. Specifically, we compare molecular dynamics with electronic friction, Ehrenfest dynamics, independent electron surface hopping, and the broadened classical master equation approach. In the case of independent electron surface hopping, we implement a simple decoherence correction approach and assess its impact on vibrationally inelastic scattering. Our results show that simple, low-dimensional models can be used to qualitatively capture experimentally observed vibrational energy transfer and provide insight into the relative performance of different MQC schemes. We observe that all approaches predict similar kinetic energy dependence but return different vibrational energy distributions. Finally, by varying the molecule-metal coupling, we can assess the coupling regime in which some MQC methods become unsuitable.

Precision electron measurements in the solar wind at 1 au from NASA’s Wind spacecraft

Context. The non-equilibrium characteristics of electron velocity distribution functions (eVDFs) in the solar wind are key to understanding the overall plasma thermodynamics as well as the origin of the solar wind. More generally, they are important in understanding heat conduction and energy transport in all weakly collisional plasmas. Solar wind electrons are not in local thermodynamic equilibrium, and their multicomponent eVDFs develop various non-thermal characteristics, such as velocity drifts in the proton frame and temperature anisotropies as well as suprathermal tails and heat fluxes along the local magnetic field direction. Aims. This work aims to characterize precisely and systematically the nonthermal characteristics of the eVDF in the solar wind at 1 au using data from the Wind spacecraft. Methods. We present a comprehensive statistical analysis of solar wind electrons at 1 au using the electron analyzers of the 3D-Plasma instrument on board Wind. This work uses a sophisticated algorithm developed to analyze and characterize separately the three populations – core, halo and strahl – of the eVDF up to super-halo energies (2 keV). This algorithm calibrates these electron measurements with independent electron parameters obtained from the quasi-thermal noise around the electron plasma frequency measured by Wind’s Thermal Noise Receiver (TNR). The code determines the respective set of total electron, core, halo, and strahl parameters through non-linear least-square fits to the measured eVDF, properly taking into account spacecraft charging and other instrumental effects, such as the incomplete sampling of the eVDF by particle detectors. Results. We use four years, approximately 280 000 independent measurements, of core, halo, and strahl electron parameters to investigate the statistical properties of these different populations in the slow and fast solar wind. We discuss the distributions of their respective densities, drift velocities, temperature, and temperature anisotropies as functions of solar wind speed. We also show distributions with solar wind speed of the total density, temperature, temperature anisotropy, and heat flux of the total eVDF, as well as those of the proton temperature, proton-to-electron temperature ratio, proton-β and electron-β. Intercorrelations between some of these parameters are also discussed. Conclusions. The present data set represents the largest, high-precision collection of electron measurements in the pristine solar wind at 1 au. It provides a new wealth of information on electron microphysics. Its large volume will enable future statistical studies of parameter combinations and their dependences under different plasma conditions.

Towards building a unified adsorption model for goethite based on direct measurements of crystal face compositions: I. Acidity behavior and As(V) adsorption

We have determined the proton, electrolyte (NaNO3) and arsenate affinity constants on the corresponding surface sites of goethite. An empirical optimization approach was applied using the Charge Distribution Multisite Complexation (CD-MUSIC) model, initially, by simulating an extensive proton adsorption data set obtained from four goethites of specific surface areas (SSAs) spanning from 43 to 89 m2/g. Each goethite showed different crystal face compositions, which were measured previously from independent high resolution electron microscopy observations. Only the capacitance value was left as an additional optimizing parameter. For arsenate adsorption, with the above optimized values fixed, the contributing surface arsenate complexes and their respective affinity constants and charge distributions (CD) were also optimized. A unified set of affinity and CD parameters was obtained, where the only resulting variables among goethites were the capacitance 1, the specific surface area and the crystal face contributions (and thus their reactive surface site densities).It was found that the site density parameter is decisive when data show adsorption maxima, such as in the arsenate adsorption isotherms. The self-consistent modeling approach yielded pKa values of singly-coordinated sites of 8.82, and of triply-coordinated sites of 9.65. Three surface arsenate complexes bound only to singly-coordinated sites were found to describe all experimental data, although only two of them were predominant across the pH and As(V) concentration ranges investigated: a bidentate non protonated (BD) complex, and a protonated monodentate (HMD) one. Charge distribution of surface arsenate complexes was found to significantly influence the optimizations, but increased values of optimized capacitance 1 were found to compensate for previously underestimated surface site density values, to yield almost identical surface affinity and CD parameters.Finally, correlations found between surface site density and capacitance-1 parameters with SSA expanded the applicability of the modeling approach presented, to other goethites with different SSAs than the ones investigated here.

K-shell X-ray production cross sections of Ti, Cr, Ni and Zn induced by chlorine ions

In this work we report on the results of the total K-shell X-ray production cross sections of Ti, Cr, Ni and Zn induced by Cl4+ and Cl5+ ions with energies ranging from 4 MeV to 10 MeV. The experimental results were compared with Atomic Orbitals Coupled-Channels (CC) calculations based on the independent electron model. The experimental X-ray production cross sections vary from about 10−2 barns for Zn up to 102 barns for Ti. The results obtained for Ti indicate that the present CC calculations underestimate the experimental cross sections up to two orders of magnitude at 10 MeV chlorine bombarding energy. However, the discrepancy between CC calculations and experimental results decreases as both bombarding energy and the atomic number of the target species increase. The dependency of the experiment-theory agreement on the asymmetry and adiabaticity parameters α and η respectively is discussed.

Prachařite, CaSb5+2(As3+2O5)2O2·10H2O, a new mineral from Lavrion, Greece

Prachařite, ideally CaSb5+2(As3+2O5)2O2·10H2O, is a new mineral found in underground workings of the Plaka Mine No. 80, Plaka, Lavrion Mining District, Attica, Greece. It occurs as colourless to white, thin tabular hexagonal, in general sharp crystals up to 2.5 mm in diameter, and is associated with pharmacolite, sulphur and very rare smamite {Ca2Sb(OH)4[H(AsO4)2]·6H2O} on a matrix composed of sphalerite, galena and carbonate gangue. Prachařite is translucent to transparent, with a glassy lustre, white streak, a good cleavage parallel to {0001} and a distinct cleavage parallel to {10overline{1 }0}. It is non-luminescent, brittle, and has an uneven fracture, a Mohs hardness of 2–2.5 and X-ray density Dx = 2.848 g/cm3, Dcalc. = 2.836–2.853 g/cm3 (for two measured compositions). Optically, it is uniaxial negative, with ω = 1.619(1) and ε = 1.553(1). Prachařite is trigonal, space group Poverline{3 }c1 (no. 165), with a = 13.951(2), c = 19.899(2) Å, V = 3354.1(10) Å3 and Z = 6. Strongest lines in the X-ray powder diffraction pattern are [d in Å (I) hkl]: 9.894 (100) 002; 6.045 (8) 200; 5.156 (10) 202; 4.946 (11) 004; 3.297 (19) 311, 006, 222; 2.988 (22) 400, 313, 116. Two sets of independent electron probe micro-analyses yielded (wt%): CaO 6.28/7.12, MgO 0.09/-, Zn -/0.01, Sb2O5 39.22/40.19, As2O3 47.59/47.39, SO3 -/0.02, H2O 21.65/22.04 (calculated on the basis of ideal composition derived from crystal-structure determination), total 114.83/116.77; the total is reproducibly high due to a loss of a third of all water molecules under the electron beam. The empirical formulae, based on O = 22 atoms per formula unit, for the two datasets are very similar, (Ca0.93Mg0.02)Σ0.95Sb2.02(AsO3)4.00·10H2O and Ca1.04Sb2.03(AsO3)3.92·10H2O. The ideal formula is CaSb5+2(As3+2O5)2O2·10H2O, determined with the help of a crystal-structure determination based on single-crystal X-ray diffraction datasets collected at room temperature (R1 = 2.3%). The atomic arrangement of prachařite is unusual; it is based on two different layers containing a six-membered ring of corner-sharing SbO6 octahedra, an eight-coordinated Ca1 atom in the centre of the ring, two non-equivalent AsO3 groups corner-linked to form a (As2O5)4− diarsenite group, and, on interlayer sites, a seven-coordination Ca2 atom and three water molecules (all only weakly hydrogen-bonded), one of which is only partially occupied (split position). The mineral is named in honour of Dr Ivan Prachař, a long-term researcher of the mineralogy and underground workings of Lavrion.

Metal-Induced Fast Vibrational Energy Relaxation: Quantum Nuclear Effects Captured in Diabatic Independent Electron Surface Hopping (IESH-D) Method.

In this paper, we propose a simple approach to include quantum nuclear effects in the weak electronic coupling regime within the independent electron surface hopping (IESH) method for simulating nonadiabatic dynamics near metal surfaces. Our method uses electronic states in a diabatic basis, and electronic transitions between metal and molecular states are included using Landau-Zener theory. We benchmark our novel approach using a two-state model system for which exact results (obtained from Fermi's golden rule) are available. We further investigate the effect of metallic electrons on the rate and the pathway of vibrational energy relaxation.

Efficient implementation and performance analysis of the independent electron surface hopping method for dynamics at metal surfaces.

Independent electron surface hopping (IESH) is a computational algorithm for simulating the mixed quantum-classical molecular dynamics of adsorbate atoms and molecules interacting with metal surfaces. It is capable of modeling the nonadiabatic effects of electron-hole pair excitations on molecular dynamics. Here, we present a transparent, reliable, and efficient implementation of IESH, demonstrating its ability to predict scattering and desorption probabilities across a variety of systems, ranging from model Hamiltonians to full dimensional atomistic systems. We further show how the algorithm can be modified to account for the application of an external bias potential, comparing its accuracy to results obtained using the hierarchical quantum master equation. Our results show that IESH is a practical method for modeling coupled electron-nuclear dynamics at metal surfaces, especially for highly energetic scattering events.

Probing Methyl Group Tunneling in [(CH3)2NH2][Zn(HCOO)3] Hybrid Perovskite Using Co2+ EPR.

At low temperature, methyl groups act as hindered quantum rotors exhibiting rotational quantum tunneling, which is highly sensitive to a local methyl group environment. Recently, we observed this effect using pulsed electron paramagnetic resonance (EPR) in two dimethylammonium-containing hybrid perovskites doped with paramagnetic Mn2+ ions. Here, we investigate the feasibility of using an alternative fast-relaxing Co2+ paramagnetic center to study the methyl group tunneling, and, as a model compound, we use dimethylammonium zinc formate [(CH3)2NH2][Zn(HCOO)3] hybrid perovskite. Our multifrequency (X-, Q- and W-band) EPR experiments reveal a high-spin state of the incorporated Co2+ center, which exhibits fast spin-lattice relaxation and electron spin decoherence. Our pulsed EPR experiments reveal magnetic field independent electron spin echo envelope modulation (ESEEM) signals, which are assigned to the methyl group tunneling. We use density operator simulations to extract the tunnel frequency of 1.84 MHz from the experimental data, which is then used to calculate the rotational barrier of the methyl groups. We compare our results with the previously reported Mn2+ case showing that our approach can detect very small changes in the local methyl group environment in hybrid perovskites and related materials.