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Accurate electronic structure calculations are essential in modern materials science, but strongly correlated systems pose a significant challenge due to their computational cost. Traditional methods, such as complete active space self-consistent field (CASSCF), scale exponentially with system size, while alternative methods like the density matrix renormalization group (DMRG) scale more favorably, yet remain limited for large systems. In this work, we demonstrate how a simple machine learning model can enhance quantum chemical DMRG calculations, improving their accuracy to chemical precision, even for systems that would otherwise require considerably higher computational resources. The systems under study are polycyclic aromatic hydrocarbons, which are typical candidates for DMRG calculations and are highly relevant for advanced technological applications.

Following the recent observation of anomalous Hall effect in antiferromagnetic hexagonal MnTe thin films, related phenomena at finite frequencies have come into focus. Magnetic circular dichroism (MCD) is the key material property here. In the x-ray range, the XMCD has already been demonstrated and used to visualise domains via photoemission electron microscopy (PEEM). Here we report on MCD in optical range and discuss its microscopic mechanism., Comment: paper associated with presentation at 36th ICPS, Ottawa

The Density Matrix Renormalization Group (DMRG) method has become a prominent tool for simulating strongly correlated electronic systems characterized by dominant static correlation effects. However, capturing the full scope of electronic interactions, especially for complex chemical processes, requires an accurate treatment of static and dynamic correlation effects, which remains a significant challenge in computational chemistry. This study presents a new approach integrating a Hermitian coupled-cluster-based downfolding technique, incorporating dynamic correlation into active-space Hamiltonians, with the DMRG method. By calculating the ground-state energies of these effective Hamiltonians via DMRG, we achieve a more comprehensive description of electronic structure. We demonstrate the accuracy and efficiency of this combined method for advancing simulations of strongly correlated systems using benchmark calculations on molecular systems, including N$_2$, benzene, and tetramethyleneethane (TME).

The emerging field of polaritonic chemistry explores the behavior of molecules under strong coupling with cavity modes. Despite recent developments in ab initio polaritonic methods for simulating polaritonic chemistry under electronic strong coupling, their capabilities are limited, especially in cases where the molecule also features strong electronic correlation. To bridge this gap, we have developed a novel method for cavity QED calculations utilizing the Density Matrix Renormalization Group (DMRG) algorithm in conjunction with the Pauli-Fierz Hamiltonian. Our approach is applied to investigate the effect of the cavity on the S0 -S1 transition of n-oligoacenes, with n ranging from 2 to 5, encompassing 22 fully correlated {\pi} orbitals in the largest pentacene molecule. Our findings indicate that the influence of the cavity intensifies with larger acenes. Additionally, we demonstrate that, unlike the full determinantal representation, DMRG efficiently optimizes and eliminates excess photonic degrees of freedom, resulting in an asymptotically constant computational cost as the photonic basis increases.

We demonstrate the possibility of growing textured La$_{2/3}$Sr$_{1/3}$MnO$_3$ (LSMO) thin films on silicon substrates with magneto-optical and optical properties comparable to high-quality epitaxial layers grown on bulk SrTiO$_3$ (STO). The pulsed laser deposition growth of LSMO is achieved by a two-dimensional nanosheet (NS) seed layer of Ca$_2$Nb$_3$O$_{10}$ (CNO) inducing epitaxial stabilization of LSMO films. The resulting layers possess a higher Curie temperature and a lower overall magnetization than samples of LSMO on STO. Spectra of the full permittivity tensor were calculated from optical and magneto-optical measurements. Spectral dependencies of both the diagonal and off-diagonal elements share many similarities between the LSMO/NS/Si and LSMO/STO samples. These similarities indicate comparable electronic structures of the layers and demonstrate comparable optical quality of textured LSMO on NS/Si and epitaxial LSMO on STO.

In this work we integrate the variational quantum eigensolver (VQE) with the adiabatic connection (AC) method for efficient simulations of chemical problems on near-term quantum computers. Orbital optimized VQE methods are employed to capture the strong correlation within an active space and classical AC corrections recover the dynamical correlation effects comprising electrons outside of the active space. On two challenging strongly correlated problems, namely the dissociation of N$_2$ and the electronic structure of the tetramethyleneethane biradical, we show that the combined VQE-AC approach enhances the performance of VQE dramatically. Moreover, since the AC corrections do not bring any additional requirements on quantum resources or measurements, they can literally boost the VQE algorithms. Our work paves the way towards quantum simulations of real-life problems on near-term quantum computers.

The presented work is focused on the optical and magneto-optical characterization of TeO2-ZnO-BaO (TZB) tellurite glasses. We investigated the refractive index and extinction coefficient dispersion by spectroscopic ellipsometry from ultraviolet, 0.193 um, up to mid infrared, 25 um spectral region. Studied glasses exhibited large values of linear (n632 = 1.91-2.09) and non-linear refractive index (n2 = 1.20-2.67x10-11 esu), Verdet constant (V632 = 22-33 radT-1m-1) and optical band gap energy (Eg = 3.7-4.1 eV). The materials characterization revealed that BaO substitution by ZnO leads (at constant content of TeO2) to an increase in linear and nonlinear refractive index as well as Verdet constant while the optical band gap energy decreases. Fiber drawing ability of TeO2-ZnO-BaO glassy system has been demonstrated on 60TeO2-20ZnO-20BaO glass with presented mid infrared attenuation coefficient. Specific parameters such as dispersion and single oscillator energy, Abbe number, and first-/ third-order optical susceptibility are enclosed together with the values of magneto-optic anomaly derived from the calculation of measured dispersion of the refractive index.

The new generation of proposed light-emitting molecules for OLEDs has raised a considerable research interest due to its exceptional feature-a negative singlet-triplet (ST) gap violating the Hund's multiplicity rule in the excited S1 and T1 states. We investigate the role of spin polarization in the mechanism of ST gap inversion. Spin polarization is associated with doubly excited determinants of certain types, whose presence in the wavefunction expansion favors the energy of the singlet state more than that of the triplet. Using a perturbation theory-based model for spin polarization, we propose a simple descriptor for prescreening of candidate molecules with negative ST gaps and prove its usefulness for heptazine-type molecules. Numerical results show that the quantitative effect of spin polarization is approximately inverse-proportional to the HOMO-LUMO exchange integral. Comparison of single- and multireference coupled- cluster predictions of ST gaps shows that the former methods provide good accuracy by correctly balancing the effects of doubly excited determinants and dynamic correlation. We also show that accurate ST gaps may be obtained using a complete active space model supplemented with dynamic correlation from multireference adiabatic connection theory.

Open-shell benzenoid polycyclic aromatic hydrocarbons, known as magnetic nanographenes, exhibit unconventional p-magnetism arising from topological frustration or strong electronic-electron (e-e) interaction. Imprinting multiple strongly entangled spins into polyradical nanographenes creates a major paradigm shift in realizing non-trivial collective quantum behaviors and exotic quantum phases in organic quantum materials. However, conventional design approaches are limited by a single magnetic origin, which can restrict the number of correlated spins or the type of magnetic ordering in open-shell nanographenes. Here, we present a novel design strategy combing topological frustration and e-e interactions to fabricate the largest fully-fused open-shell nanographene reported to date, a 'butterfly'-shaped tetraradical on Au(111). We employed bond-resolved scanning tunneling microscopy and spin excitation spectroscopy to unambiguously resolve the molecular backbone and reveal the strongly correlated open-shell character, respectively. This nanographene contains four unpaired electrons with both ferromagnetic and anti-ferromagnetic interactions, harboring a many-body singlet ground state and strong multi-spin entanglement, which can be well described by many-body calculations. Furthermore, we demonstrate that the nickelocene magnetic probe can sense highly-correlated spin states in nanographene. The ability to imprint and characterize many-body strongly correlated spins in polyradical nanographenes not only presents exciting opportunities for realizing non-trivial quantum magnetism and phases in organic materials but also paves the way toward high-density ultrafast spintronic devices and quantum information technologies., Comment: 17 pages, 4 figures

The DMRG method, despite its favorable scaling, it is in practice not suitable for computations of dynamic correlation. Several approaches to include that in post-DMRG methods exist; in our group we focused on the tailored-CC (TCC) approach. This method works well in many situations, however, in exactly degenerate cases (with two or more determinants of equal weight), it exhibits a bias towards the reference determinant representing the Fermi vacuum. Although in some cases it is possible to use a compensation scheme to avoid this bias for energy differences, as we did in a previous work on the singlet-triplet gap in the tetramethylenethane (TME) molecule, it is certainly a drawback. In order to overcome the single-reference bias of the TCC method, we have developed a Hilbert-space multireference version of tailored CC, which can treat several determinants on an equal footing. We have employed a multireference analysis of the DMRG wave function in the matrix product state form to get the active amplitudes for each reference determinant and their constant contribution to the effective Hamiltonian. We have implemented and compared the performance of three Hilbert-space MRCC variants - the state universal one, and the Brillouin-Wigner and Mukherjee's state specific ones. We have assessed these approaches on the cyclobutadiene and tetramethylenethane (TME) molecules, which are both diradicals with exactly degenerate determinants at a certain geometry. Two DMRG active spaces have been selected based on orbital entropies, while the MRCC active space comprised the HOMO and LUMO orbitals needed for description of the diradical. We have also investigated the sensitivity of the results on orbital rotation of the HOMO-LUMO pair, as it is well known that Hilbert-space MRCC methods are not invariant to such transformations.

Growth optimization of multilayers is a topic of interest due to their unique physical properties. Systems containing magnetic materials, such as platinum-cobalt, have been studied because of their potential for technological applications, e.g. spintronics, magnetic storage and magnetic sensors. Since the magnetic properties of thin layers are strongly related to the growth parameters, the fine tuning of these parameters is necessary to produce multilayers with specific properties required in various applications. Here, an efficient approach to tune the coercive field of Co ultrathin films in the multilayer by varying the underlayer thickness is demonstrated. Using magnetron sputtering, we prepared multilayer systems of Au(x)/Pt(5nm)/Co(0.7nm)/Au(5nm) with various thicknesses of Au underlayer. The surface morphology of Au(x)/Pt(5nm) stack on which Co layer was deposited was studied by atomic force microscopy. We show the possibility to control the interfacial roughness by changing the Au underlayer thickness due to its island-like growth mechanism (Volmer-Weber mode). As the nominal thickness of Au increases, the islands grow in larger lateral size, resulting in a higher overall roughness of the layer surface. Magnetization measurements indicate a direct influence of the underlayer roughness on the coercivity of the multilayers by promoting additional magnetic anisotropy. With thickness of the Au layer up to 20 nm, we can change the coercive field in the range from ~200 Oe to ~1100 Oe, while remaining a nearly constant saturation magnetization. The use of Cu replacing Au underlayer in the same multilayers was also investigated, demonstrating the possibility of coercivity adjustment using different materials. The results are important for applications where the magnetic properties of multilayer structures based on Co thin films could be adjusted via buffer layer roughness engineering., Comment: 15 pages, 8 figures

The anomalous Nernst effect (ANE) is a member of the extensive family of topological effects in solid state physics. It converts a heat current into electric voltage and originates from the Berry curvature of electronic bands near the Fermi level. Recent results established the Fe$_3$Ga alloy as one of the most promising candidates for applications, due to its flat band structure consisting of rich web of nodal lines. In this theoretical work, we study the effect of deformation of Fe$_3$Ga on the anomalous Nernst effect, which naturally occurs in thin films. Furthermore, we demonstrate that doping, which effectively shifts the position of the Fermi level, can also significantly modify the strength of the effect. Lastly, we provide detailed analysis of the origin of ANE in the electronic structure of Fe$_3$Ga which yields a deeper insight into the generating mechanisms, understanding of which can lead to substantial enhancement of the effect in the future.

We report on magneto-optical studies of the quasi-two-dimensional van der Waals antiferromagnet FePS$_3$. Our measurements reveal an excitation that closely resembles the antiferromagnetic resonance mode typical of easy-axis antiferromagnets, nevertheless, it displays an unusual, four-times larger Zeeman splitting in an applied magnetic field. We identify this excitation with an $|S_z|=4$ multipolar magnon -- a single-ion 4-magnon bound state -- that corresponds to a full reversal of a single magnetic moment of the Fe$^{2+}$ ion. We argue that condensation of multipolar magnons in large-spin materials with a strong magnetic anisotropy can produce new exotic states., Comment: 7 pages, 3 figures + supplement

The density matrix renormalization group (DMRG) method has already proved itself as a very efficient and accurate computational method, which can treat large active spaces and capture the major part of strong correlation. Its application on larger molecules is, however, limited by its own computational scaling as well as demands of methods for treatment of the missing dynamical electron correlation. In this work, we present the first step in the direction of combining DMRG with density functional theory (DFT), one of the most employed quantum chemical methods with favourable scaling, by means of the projection-based wave function (WF)-in-DFT embedding. On the two proof-of-concept but important molecular examples, we demonstrate that the developed DMRG-in-DFT approach provides a very accurate description of molecules with a strongly correlated fragment.

A multiconfigurational adiabatic connection (AC) formalism is an attractive approach to computing dynamic correlation within CASSCF and DMRG models. Practical realizations of AC have been based on two approximations: i) fixing one- and two-electron reduced density matrices (1- and 2-RDMs) at the zero-coupling constant limit and ii) extended random phase approximation (ERPA). This work investigates the the effect of removing the "fixed-RDM" approximation in AC. The analysis is carried out for two electronic Hamiltonian partitionings: the group product function- and the Dyall-Hamiltonians. Exact reference AC integrands are generated from the DMRG FCI solver. Two AC models are investigated, employing either exact 1- and 2-RDMs or their second-order expansions in the coupling constant in the ERPA equations. Calculations for model molecules indicate that lifting the fixed-RDM approximation is a viable way toward improving accuracy of the existing AC approximations.

Magnetic layered materials have emerged recently as promising systems to introduce magnetism in structures based on two-dimensional (2D) materials and to investigate exotic magnetic ground states in the 2D limit. In this work, we apply high hydrostatic pressures up to P = 8.7 GPa to the bulk layered antiferromagnet FePS$_3$ to tune the collective lattice excitations (phonons) in resonance with magnetic excitations (magnons). Close to P = 4 GPa, the magnon-phonon resonance is achieved and the strong coupling between these collective modes leads to the formation of new quasi-particles, the magnon-polarons, evidenced in our low temperature Raman scattering experiments by a particular avoided crossing behavior between the phonon and the doubly degenerate antiferromagnetic magnon. At the pressure-induced magnon-phonon resonance, three distinct coupled modes emerge. As it is mainly defined by intralayer properties, we show that the energy of the magnon is nearly pressure independent. We additionally apply high magnetic fields up to B = 30 T to fully identify and characterize the magnon excitations, and to explore the different magnon-polaron regimes for which the phonon has an energy lower-, equal to-, or higher- than the magnon energy. The description of our experimental data requires introducing a phonon-phonon coupling not taken into account in actual calculations., Comment: 11 pages + 6 pages of supplementary materials

Strong correlation can be essentially captured with multireference wavefunction methods such as complete active space self-consistent field (CASSCF) or density matrix renormalization group (DMRG). Still, an accurate description of the electronic structure of strongly correlated systems requires accounting for the dynamic electron correlation, which CASSCF and DMRG largely miss. In this work a new approach for the correlation energy based on the adiabatic connection (AC) is proposed. The AC$_{\rm n}$ method accounts for terms up to the desired order n in the coupling constant, is rigorously size-consistent, free from instabilities and intruder states. It employs the particle-hole multireference random phase approximation and the Cholesky decomposition technique, which leads to a computational cost growing with the fifth power of the system size. Thanks to AC$_{\rm n}$ depending solely on one- and two-electron CAS reduced density matrix, the method is much more efficient than existing ab initio dynamic correlation methods for strong correlation. AC$_{\rm n}$ affords excellent results for singlet-triplet gaps of challenging organic biradicals. Development presented in this work opens new perspectives for accurate calculations of systems with dozens of strongly correlated electrons.

Here we present a magnetic thin film with a weak ferrimagnetic (FIM) phase above the N\'eel temperature ($T_{N}$ = 240 K) and a non-collinear antiferromagnetic (AFM) phase below, exhibiting a small net magnetisation due to strain-associated canting of the magnetic moments. A long-range ordered FIM phase has been predicted in related materials, but without symmetry analysis. We now perform this analysis and use it to calculate the MOKE spectra in AFM and FIM phases. From the good agreement between the form of the measured and predicted MOKE spectra, we propose the AFM and FIM phases share the magnetic space group C2'/m' and that the symmetry driven magneto-optic and magneto-transport properties are maximised at room temperature in the FIM phase due to the non-zero intrinsic Berry phase contribution present in these materials. A room temperature FIM phase with large optical and transport signatures, as well as sensitivity to lattice strain and magnetic field, has useful prospects for high-speed spintronic applications., Comment: 21 pages 4 figures 1 table 4 supplementary figures 1 supplementary table Co-first author: F. Johnson and J. Z\'azvorka Corresponding authors: L. F. Cohen and M. Veis; Typos corrected and discussion of symmetry added; title changed to be concise; text on figures made larger

We report synthesis of single crystalline NaMnAs, confirm its antiferromagnetic order and characterise the sample by photoemission spectroscopy. The electronic structure was studied using optical transmittance, x-ray and ultraviolet spectroscopy and by theoretical modeling using local density approximation (LDA) extended to LDA+U when Heisenberg model parameters were determined. Optical transmittance measurement have confirmed the theoretical predictions that NaMnAs is a semiconductor. Also the N\'eel temperature was closer determined for the first time from temperature dependence of magnetization, in agreement with our Monte Carlo simulations., Comment: 11 pages, 11 figures

The quantum chemical version of the density matrix renormalization group (DMRG) method has established itself as one of the methods of choice for calculations of strongly correlated molecular systems. Despite its great ability to capture strong electronic correlation in large active spaces, it is not suitable for computations of dynamical electron correlation. In this work, we present a new approach to the electronic structure problem of strongly correlated molecules, in which DMRG is responsible for a proper description of the strong correlation, whereas dynamical correlation is computed via the recently developed adiabatic connection (AC) technique, which requires only up to two-body active space reduced density matrices. We report encouraging results of this approach on typical candidates for DMRG computations, namely the $n$-acenes ($n = 2 \rightarrow 7$), Fe(II)-porphyrin, and Fe$_3$S$_4$ cluster.

The hybridization of magnons (spin waves) with phonons, if sufficiently strong and comprising long wavelength excitations, may offer a new playground when manipulating the magnetically ordered systems with light. Applying a magnetic field to a quasi-2D antiferromagnet, FePS3, we tune the magnon-gap excitation towards coincidence with the initially lower-in-energy phonon modes. Hybrid magnon-phonon modes, the magnon polarons are unveiled with demonstration of a pronounced avoided crossing between the otherwise bare magnon and phonon excitations. The magnon polarons in FePS3 are primary traced with Raman scattering experiments, but, as we show, they also couple directly to terahertz photons, what evokes their further explorations in the domain of antiferromagnetic optospintronics., Comment: 10 pages, 4 figures and Supplementary Materials, to be published in Phys. Rev. B

Dielectric Mie nanoresonators showing strong light-matter interaction at the nanoscale may enable new functionality in photonic devices. Recently, strong magneto-optical effects have been observed in magneto-optical nanophotonic devices due to the electromagnetic field localization. However, most reports so far have been focused on the enhancement of conventional magneto-optical effects. Here, we report the observation of circular displacement current induced anomalous magneto-optical effects in high-index-contrast Si/Ce:YIG/YIG/SiO2 Mie resonators. In particular, giant modulation of light intensity in transverse magnetic configuration up to 6.4 % under s-polarized incidence appears, which is non-existent in planar magneto-optical thin films. Apart from that, we observe a large rotation of transmitted light polarization in the longitudinal magnetic configuration under near normal incidence conditions, which is two orders of magnitude higher than for a planar magneto-optical thin film. These phenomena are essentially originated from the unique circular displacement current when exciting the magnetic resonance modes in the Mie resonators, which changes the incident electric field direction locally. Our work indicates an uncharted territory of light polarization control based on the complex modal profiles in all-dielectric magneto-optical Mie resonators and metasurfaces, which opens the door for versatile control of light propagation by magnetization for a variety of applications in vectoral magnetic field and biosensing, free space non-reciprocal photonic devices, magneto-optical imaging and optomagnetic memories.

Iron-sulfur clusters comprise an important functional motif of the catalytic centers of biological systems, capable of enabling important chemical transformations at ambient conditions. This remarkable capability derives from a notoriously complex electronic structure that is characterized by a high density of states that is sensitive to geometric changes. The spectral sensitivity to subtle geometric changes has received little attention from fully-correlated calculations, owing partly to the exceptional computational complexity for treating these large and correlated systems accurately. To provide insight into this aspect, we report the first Complete Active Space Self Consistent Field (CASSCF) calculations for different geometries of cubane-based clusters using two complementary, fully-correlated solvers: spin-pure Adaptive Sampling Configuration Interaction (ASCI) and Density Matrix Renormalization Group (DMRG). We find that the previously established picture of a double-exchange driven magnetic structure, with minute energy gaps (< 1 mHa) between consecutive spin states, has a weak dependence on the underlying geometry. However, the spin gap between the lowest singlet and the highest spin states is strongly geometry dependent, changing by an order of magnitude upon slight deformations that are still within biologically relevant parameters. The CASSCF orbital optimization procedure, using active spaces as large as 86 electrons in 52 orbitals, was found to reduce this gap by a factor of two compared to typical mean-field orbital approaches. Our results clearly demonstrate the need for performing highly correlated calculations to unveil the challenging electronic structure of these complex catalytic centers., Comment: 16 pages, 7 figures, 6 tables plus SI (12 pages, 3 figures, 9 tables)

Despite belonging to a well-studied family of transition metal trihalides, VI_3 has received significant attention only recently. As a hard ferromagnetic van der Waals compound with a large coercivity, it attracted much attention because of its potential use in atomically thin spintronic and optoelectronic devices. However, practical exploration of VI_3 is challenging due to its instability under ambient conditions. Here, we present a comprehensive set of optical, x-ray diffraction, magnetization, and ellipsometric measurements of VI3 and demonstrate that, similarly to the related van der Waals ferromagnet CrI_3, the degradation process is accelerated by the presence of moisture. The VI_3 surface was covered by selected media commonly used in physical measurements to test its stability and lower the degradation rate three times or higher, providing practical information for experimentalists interested. The decomposition study at ambient conditions shows that the VI_3 single crystal can be used for most of the bulk, magnetization, and optical measurements without any noticeable change of physical properties, as the significant degradation appears first after ~ 2 hours of exposition as illustrated, e.g., by the evolution of the ferromagnetic T_1 and T_2 transitions. The ellipsometric measurement demonstrates that even the surface remains optically stable for at least 5 minutes., Comment: 14 pages, 6 figures

We report on an infrared magneto-spectroscopy study of Pb$_{1-x}$Sn$_x$Se, a topological crystalline insulator. We have examined a set of samples, all in the inverted regime of electronic bands, with the tin composition varying from $x=0.2$ to $0.33$. Our analysis shows that the observed response, composed of a series of interband inter-Landau level excitations, can be interpreted and modelled using the relativistic-like Hamiltonian for three-dimensional massive Dirac electrons, expanded to include diagonal quadratic terms that impose band inversion. In our data, we have not found any clear signature of massless electron states that are present on the surface of Pb$_{1-x}$Sn$_x$Se crystals in the inverted regime. Reasons for this unexpected result are discussed., Comment: 11 pages, 7 figures, to be published in Phys. Rev. B

The active-space quantum chemical methods could provide very accurate description of strongly correlated electronic systems, which is of tremendous value for natural sciences. The proper choice of the active space is crucial, but a non-trivial task. In this article, we present the neural network (NN) based approach for automatic selection of active spaces, focused on transition metal systems. The training set has been formed from artificial systems composed from one transition metal and various ligands, on which we have performed DMRG and calculated single-site entropy. On the selected set of systems, ranging from small benchmark molecules up to larger challenging systems involving two metallic centers, we demonstrate that our ML models could correctly predict the importance of orbitals with the high accuracy. Also, the ML models show a high degree of transferability on systems much larger than any complex used in training procedures.

In this paper we discuss the utilization of Variational Quantum Solver (VQE) and recently introduced Generalized Unitary Coupled Cluster (GUCC) formalism for the diagonalization of downfolded/effective Hamiltonians in active spaces. In addition to effective Hamiltonians defined by the downfolding of a subset of virtual orbitals we also consider their form defined by freezing core orbitals, which enables us to deal with larger systems. We also consider various solvers to identify solutions of the GUCC equations. We use N$_2$, H$_2$O, and C$_2$H$_4$, and benchmark systems to illustrate the performance of the combined framework.

In this paper, we analyze the numerical aspects of the inherently multi-reference density matrix renormalization group (DMRG) calculations on top of the periodic Kohn-Sham density functional theory (DFT) using the complete active space (CAS) approach. Following the technical outline related to the computation of the Hamiltonian matrix elements and to the construction of the active space, we illustrate the potential of the framework by studying the vertical many-body energy spectrum of hexagonal boron nitride (hBN) nano-flakes embedding a single boron vacancy point defect with prominent multi-reference character. We investigate the consistency of the DMRG energy spectrum from the perspective of sample size, basis size, and active space selection protocol. Results obtained from standard quantum chemical atom-centered basis calculations and plane-wave based counterparts show excellent agreement. Furthermore, we also discuss the spectrum of the periodic sheet which is in good agreement with extrapolated data of finite clusters. These results pave the way toward applying DMRG method in extended correlated solid state systems, such as point qubit in wide band gap semiconductors.

Phases of matter are ubiquitous with everyday examples including solids and liquids. In reduced dimensions, particular phases, such as the two-dimensional (2D) hexatic phase and corresponding phase transitions occur. A particularly exciting example of 2D ordered systems are skyrmion lattices, where in contrast to previously studied 2D colloid systems, the skyrmion size and density can be tuned by temperature and magnetic field. This allows us to drive the system from a liquid phase to a hexatic phase as deduced from the analysis of the hexagonal order. Using coarse-grained molecular dynamics simulations of soft disks, we determine the skyrmion interaction potentials and we find that the simulations are able to reproduce the full two-dimensional phase behavior. This shows that not only the static behavior of skyrmions is qualitatively well described in terms of a simple two-dimensional model system but skyrmion lattices are versatile and tunable two-dimensional model systems that allow for studying phases and phase transitions in reduced dimensions., Comment: Corrected Acknowledgements

The Heusler compound Co$_2$MnSi provides a crystallographic transition from B2 to L2$_1$ structure with increasing annealing temperature $T_a$, being a model system for investigating the influence of crystallographic ordering on structural, magnetic, optic, and magnetooptic (MO) properties. Here, we present quadratic magnetooptic Kerr effect (QMOKE) spectra depending on $M^2$ in addition to the linear magnetooptic Kerr effect (LinMOKE) spectra being proportional to $M$, both in the extended visible spectral range of light from 0.8\,eV to 5.5\,eV. We investigated a set of Co$_2$MnSi thin films deposited on MgO(001) substrates and annealed from 300$^\circ$C to 500$^\circ$C. The amplitude of LinMOKE and QMOKE spectra scales linearly with $T_a$, and this effect is well pronounced at the resonant peaks below 2.0\,eV of the QMOKE spectra. Furthermore, the spectra of the MO parameters, which fully describe the MO response of Co$_2$MnSi up to the second order in $M$, are obtained dependend on $T_a$. Finally, the spectra are compared to ab-initio calculations of a purely L2$_1$ ordered Co$_2$MnSi Heusler compound., Comment: 4 pages, 3 figures, supplemental pdf, supplemental data files

There are three essential problems in computational relativistic chemistry: electrons moving at relativistic speeds, close lying states and dynamical correlation. Currently available quantum-chemical methods are capable of solving systems with one or two of these issues. However, there is a significant class of molecules, in which all the three effects are present. These are the heavier transition metal compounds, lanthanides and actinides with open d or f shells. For such systems, sufficiently accurate numerical methods are not available, which hinders the application of theoretical chemistry in this field. In this paper, we combine two numerical methods in order to address this challenging class of molecules. These are the relativistic versions of coupled cluster methods and density matrix renormalization group (DMRG) method. To the best of our knowledge, this is the first relativistic implementation of the coupled cluster method externally corrected by DMRG. The method brings a significant reduction of computational costs, as we demonstrate on the system of TlH, AsH and SbH.

Fe(II)-porphyrins (FeP) play an important role in many reactions relevant to material science and biological processes, due to their closely lying spin states. However, this small energetic separation also makes it challenging to establish the correct spin state ordering. Although the prevalent opinion is that these systems posses the triplet ground state, the recent experiment on Fe(II)-phthalocyanine under conditions matching those of an isolated molecule points toward the quintet ground state. We present a thorough study of FeP model by means of the density functional theory and density matrix renormalization group based tailored coupled clusters, in which we address all previously discussed correlation effects. We examine the importance of geometrical parameters, the Fe-N distances in particular, and conclude that the system possesses the quintet ground state, which is in our calculations well-separated from the triplet state.

We present, to the best of our knowlegde, the first attempt to exploit the supercomputer platform for quantum chemical density matrix renormalization group (QC-DMRG) calculations. We have developed the parallel scheme based on the in-house MPI global memory library, which combines operator and symmetry sector parallelisms, and tested its performance on three different molecules, all typical candidates for QC-DMRG calculations. In case of the largest calculation, which is the nitrogenase FeMo cofactor cluster with the active space comprising 113 electrons in 76 orbitals and bond dimension equal to 6000, our parallel approach scales up to approximately 2000 CPU cores., Comment: only acknowledgement corrected

PANDA (anti-Proton ANnihiliation at DArmstadt) is planned to be one of the four main experiments at the future international accelerator complex FAIR (Facility for Antiproton and Ion Research) in Darmstadt, Germany. It is going to address fundamental questions of hadron physics and quantum chromodynamics using cooled antiproton beams with a high intensity and and momenta between 1.5 and 15 GeV/c. PANDA is designed to reach a maximum luminosity of 2x10^32 cm^2 s. Most of the physics programs require an excellent particle identification (PID). The PID of hadronic states at the forward endcap of the target spectrometer will be done by a fast and compact Cherenkov detector that uses the detection of internally reflected Cherenkov light (DIRC) principle. It is designed to cover the polar angle range from 5{\deg} to 22{\deg} and to provide a separation power for the separation of charged pions and kaons up to 3 standard deviations (s.d.) for particle momenta up to 4 GeV/c in order to cover the important particle phase space. This document describes the technical design and the expected performance of the novel PANDA Disc DIRC detector that has not been used in any other high energy physics experiment (HEP) before. The performance has been studied with Monte-Carlo simulations and various beam tests at DESY and CERN. The final design meets all PANDA requirements and guarantees suffcient safety margins., Comment: TDR for Panda/Fair to be published

Influence of substrate miscut on magnetization dynamics in SrRuO$_3$ (SRO) thin films was studied. Two films were grown on SrTiO$_3$ substrates with high ($\sim1^{\circ}$) and low ($\sim0.1^{\circ}$) miscut angles, respectively. As expected, high miscut angle leads to suppression of multi-variant growth. By means of SQUID magnetometry, comparable relaxation effects were observed in both the multi-variant and the nearly single-variant sample. Differences in the magnetization reversal process were revealed by magnetic force microscopy. It showed that the multi-variant growth leads to higher density of defects acting as pinning or nucleation sites for magnetic domains, which consequently results in deterioration of magnetic properties. It was demonstrated that the use of high miscut substrate is important for fabrication of high quality SRO thin films with low density of crystallographic defects and excellent magnetic properties., Comment: 9 pages plus graphical abstract and highlights

A 13.56 MHz RF discharge in hydrogen was studied within the pressure range of 1-17 10 Pa, and at power range of 400-1000 W. The electron energy distribution function and 18 electron density were measured by a Langmuir probe. The gas temperature was determined by 19 the Fulcher-$\alpha$ system in pure H2, and by the second positive system of nitrogen using N2 as the 20 probing gas. The gas temperature was constant and equal to 450 $\pm$ 50 K in the Capacitively 21 Coupled Plasma mode (CCP), and it was increasing with pressure and power in the Inductively 22 Coupled Plasma mode (ICP). Also the vibrational temperature of ground state of hydrogen 23 molecules was determined to be around 3100 and 2000 $\pm$ 500 K in ICP and CCP mode, 24 respectively. The concentration of atomic hydrogen was determined by means of actinometry, 25 either by using Ar (5 %) as the probing gas, or by using H2 as the actinometer in pure hydrogen 26 (Q1 rotational line of Fulcher-$\alpha$ system) The concentration of hydrogen density was increasing 27 with pressure in both modes, but with a dissociation degree slightly higher in the ICP mode (a 28 factor 2). 29 30 Submitted to Physica Scripta 31

We present a new implementation of DMRG-based tailored coupled clusters method (TCCSD), which employs the domain-based local pair natural orbital approach (DLPNO-TCCSD). Compared to the previous LPNO version of the method, the new implementation is more accurate, offers more favorable scaling and provides more consistent behavior across the variety of systems. On top of the singles and doubles, we include the perturbative triples correction (T), which is able to retrieve even more dynamic correlation. The methods were tested on three systems: tetramethyleneethane, oxo-Mn(Salen) and Iron(II)-porphyrin model. The first two were revisited to assess the performance with respect to LPNO-TCCSD. For oxo-Mn(Salen), we retrieved between 99.8-99.9% of the total canonical correlation energy which is the improvement of 0.2% over the LPNO version in less than 63% of the total LPNO runtime. Similar results were obtained for Iron(II)-porphyrin. When the perturbative triples correction was employed, irrespective of the active space size or system, the obtained energy differences between two spin states were within the chemical accuracy of 1 kcal/mol using the default DLPNO settings., Comment: Updated version: 15 pages. arXiv admin note: text overlap with arXiv:1905.06833

Tensor network methods have progressed from variational techniques based on matrix-product states able to compute properties of one-dimensional condensed-matter lattice models into methods rooted in more elaborate states such as projected entangled pair states aimed at simulating the physics of two-dimensional models. In this work, we advocate the paradigm that for two-dimensional fermionic models, matrix-product states are still applicable to significantly higher accuracy levels than direct embeddings into one-dimensional systems allow for. To do so, we exploit schemes of fermionic mode transformations and overcome the prejudice that one-dimensional embeddings need to be local. This approach takes the insight seriously that the suitable exploitation of both the manifold of matrix-product states and the unitary manifold of mode transformations can more accurately capture the natural correlation structure. By demonstrating the residual low levels of entanglement in emerging modes, we show that matrix-product states can describe ground states strikingly well. The power of the approach is exemplified by investigating a phase transition of spin-less fermions for lattice sizes up to 10x10., Comment: 9 pages, 8 figures, new material presented

We introduce a new implementation of the coupled cluster method tailored by matrix product states wave functions (DMRG-TCCSD), which employs the local pair natural orbital approach (LPNO). By exploiting locality in the coupled cluster stage of the calculation, we were able to remove some of the limitations that hindered the application of the canonical version of the method to larger systems and/or with larger basis sets. We assessed the accuracy of the approximation using two systems: tetramethyleneethane (TME) and oxo-Mn(Salen). Using the default cut-off parameters, we were able to recover over 99.7% and 99.8% of canonical correlation energy for the triplet and singlet state of TME respectively. In case of oxo-Mn(Salen), we found out that the amount of retrieved canonical correlation energy depends on the size of the active space (CAS) - we retrieved over 99.6% for the larger 27 orbital CAS and over 99.8% for the smaller 22 orbital CAS. The use of LPNO-TCCSD allowed us to perform these calculations up to quadruple-$\zeta$ basis set amounting to 1178 basis functions. Moreover, we examined dependance of the ground state of oxo-Mn(Salen) on CAS composition. We found out that the inclusion of 4d$_{xy}$ orbital plays an important role in stabilizing the singlet state at the DMRG-CASSCF level via double-shell effect. However, by including dynamic correlation the ground state was found to be triplet regardless of the size of the basis set or composition of CAS, which is in agreement with previous findings by canonical DMRG-TCCSD in smaller basis.

The magnetooptic Kerr effect (MOKE) is a well known and handy tool to characterize ferro-, ferri- and antiferromagnetic materials. Many of the MOKE techniques employ effects solely linear in magnetization $\bm{M}$. Nevertheless, a higher-order term being proportional to $\bm{M}^2$ and called quadratic MOKE (QMOKE) can additionally contribute to the experimental data. Here, we present detailed QMOKE spectroscopy measurements in the range of 0.8 -- 5.5\,eV based on a modified 8-directional method applied on ferromagnetic bcc Fe thin films grown on MgO substrates. From the measured QMOKE spectra, two further complex spectra of the QMOKE parameters $G_s$ and $2G_{44}$ are yielded. The difference between those two parameters, known as $\Delta G$, denotes the strength of the QMOKE anisotropy. Those QMOKE parameters give rise to the QMOKE tensor $\bm{G}$, fully describing the perturbation of the permittivity tensor in the second order in $\bm{M}$ for cubic crystal structures. We further present experimental measurements of ellipsometry and linear MOKE spectra, wherefrom permittivity in the zeroth and the first order in $\bm{M}$ are obtained, respectively. Finally, all those spectra are described by ab-initio calculations., Comment: 15 pages + references, , 15 Figures

Recently, the correlation theory of the chemical bond was developed, which applies concepts of quantum information theory for the characterization of chemical bonds, based on the multiorbital correlations within the molecule. Here for the first time, we extend the use of this mathematical toolbox for the description of electron-deficient bonds. We start by verifying the theory on the textbook example of a molecule with three-center two-electron bonds, namely the diborane(6). We then show that the correlation theory of the chemical bond is able to properly describe bonding situation in more exotic molecules which have been synthetized and characterized only recently, in particular the diborane molecule with four hydrogen atoms [diborane(4)] and neutral zerovalent s-block beryllium complex, whose surprising stability was attributed to a strong three-center two-electron $\pi$ bond stretching across the C-Be-C core. Our approach is of a high importance especially in the light of a constant chase after novel compounds with extraordinary properties where the bonding is expected to be unusual.

Practical challenges in simulating quantum systems on classical computers have been widely recognized in the quantum physics and quantum chemistry communities over the past century. Although many approximation methods have been introduced, the complexity of quantum mechanics remains hard to appease. The advent of quantum computation brings new pathways to navigate this challenging complexity landscape. By manipulating quantum states of matter and taking advantage of their unique features such as superposition and entanglement, quantum computers promise to efficiently deliver accurate results for many important problems in quantum chemistry such as the electronic structure of molecules. In the past two decades significant advances have been made in developing algorithms and physical hardware for quantum computing, heralding a revolution in simulation of quantum systems. This article is an overview of the algorithms and results that are relevant for quantum chemistry. The intended audience is both quantum chemists who seek to learn more about quantum computing, and quantum computing researchers who would like to explore applications in quantum chemistry., Comment: 194 pages, 13 figures, 5 tables and 404 references. Fixed formatting issues from the previous version. Comments welcome