Separable Approximation Research Articles

Cluster Perturbation Theory for Core Excited States and Core Ionization Potentials Using Core-Valence Separation.

The development of accurate and fast computational procedures for the ab initio calculation of X-ray spectroscopies is paramount to facilitate theoretical analysis of modern X-ray experiments on molecules. Herein, we present the extension of Cluster Perturbation theory to comprehend the calculation of core excited states and core ionization potentials using the core-valence separation approximation, which has seen widespread success for various quantum chemistry methods. We derive the theoretical framework for introducing core-valence separation into Cluster Perturbation series for excitation energies and display the performance of the methodology in S(D) orbital excitation spaces. The obtained core excitation energies on a test set of medium sized organic molecules show that carbon, nitrogen, and oxygen K-edge excitation energies can be determined with errors below 2 eV relative to the CCSD reference results using the developed CPS(D) excitation energy models which can be used for systems way beyond the reach of conventional CCSD.

Testing covariance separability for continuous functional data

Analyzing the covariance structure of data is a fundamental task of statistics. While this task is simple for low‐dimensional observations, it becomes challenging for more intricate objects, such as multi‐variate functions. Here, the covariance can be so complex that just saving a non‐parametric estimate is impractical and structural assumptions are necessary to tame the model. One popular assumption for space‐time data is separability of the covariance into purely spatial and temporal factors. In this article, we present a new test for separability in the context of dependent functional time series. While most of the related work studies functional data in a Hilbert space of square integrable functions, we model the observations as objects in the space of continuous functions equipped with the supremum norm. We argue that this (mathematically challenging) setup enhances interpretability for users and is more in line with practical preprocessing. Our test statistic measures the maximal deviation between the estimated covariance kernel and a separable approximation. Critical values are obtained by a non‐standard multiplier bootstrap for dependent data. We prove the statistical validity of our approach and demonstrate its practicability in a simulation study and a data example.

Nonadiabatic Tunneling in Chemical Reactions.

Quantum tunneling can have a dramatic effect on chemical reaction rates. In nonadiabatic reactions such as electron transfers or spin crossovers, nuclear tunneling effects can be even stronger than for adiabatic proton transfers. Ring-polymer instanton theory enables molecular simulations of tunneling in full dimensionality and has been shown to be far more reliable than commonly used separable approximations. First-principles instanton calculations predict significant nonadiabatic tunneling of heavy atoms even at room temperature and give excellent agreement with experimental measurements for the intersystem crossing of two nitrenes in cryogenic matrix isolation, the spin-forbidden relaxation of photoexcited thiophosgene in the gas phase, and singlet oxygen deactivation in water at ambient conditions. Finally, an outlook of further theoretical developments is discussed.

Supercontinuum laser-based gonio-scatterometer for in and out-of-plane spectral BRDF measurements.

The hyperspectral component of bidirectional reflectance measurements, namely from several hundred wavelengths upwards, is attracting growing interest for numerous applications in both optics and computer graphics. In this paper, we present a motorized hyperspectral bidirectional reflectance measurement bench that performs in-plane and out-of-plane measurements for isotropic materials using a supercontinuum laser covering the visible and near infrared range, with a sub-nanometer spectral accuracy. We describe the complete data processing chain, including a method for assessing the alignment error of the measurement bench. From these measurements, we verify the principles of non-negativity, energy conservation and Helmholtz reciprocity. We introduce criteria also to evaluate the validity of the Lambertian hypothesis for the bidirectional reflectance and its deviation from reciprocity, obtained from the measurements directly. We show the need for spectral bidirectional reflectance measurements for certain materials, rejecting the separable function approximation.

Approximate linear programming for a queueing control problem

Admission decisions for loss systems accessed by multiple customer classes are a classical queueing control problem with a wide variety of applications. When a server is available, the decision is whether to admit an arriving customer and collect a lump-sum revenue. The system can be modeled as a continuous-time infinite-horizon dynamic program, but suffers from the curse of dimensionality when different customer classes have different service rates. We use approximate linear programming to solve the problem under three approximation architectures: affine, separable piecewise linear and finite affine. The finite affine approximation is a recently proposed generalization of the affine approximation, which allows for non-stationary parameters. For both affine and finite affine approximations, we derive equivalent, but more compact, formulations that can be efficiently solved. We propose a column generation algorithm for the separable piecewise linear approximation. Our numerical results show that the finite affine approximation can obtain the tightest bounds for 75% of the instances among the three approximations. Especially, when the number of servers is large and/or the load on the system is high, the finite affine approximation always achieves the tightest bounds. Regarding policy performance, the finite affine approximation has the best performance on average compared to the other two approximations and the achievable performance region method (Bertsimaset al., 1994, Kumar and Kumar, 1994). Furthermore, the finite affine approximation is 4 to 5 orders of magnitude faster than the achievable performance region method and the separable piecewise linear approximation for large-scale instances. Therefore, considering bounds, policy performance, and computational efficiency, the finite affine approximation emerges as a competitive approximation architecture for the class of problems studied here.

Core Binding Energy Calculations: A Scalable Approach with the Quantum Embedding-Based Equation-of-Motion Coupled-Cluster Method.

We investigated the use of density matrix embedding theory to facilitate the computation of core ionization energies (IPs) of large molecules at the equation-of-motion coupled-cluster singles doubles with perturbative triples (EOM-CCSD*) level in combination with the core-valence separation (CVS) approximation. The unembedded IP-CVS-EOM-CCSD* method with a triple-ζ basis set produced ionization energies within 1 eV of experiment with a standard deviation of ∼0.2 eV for the core65 data set. The embedded variant contributed very little systematic error relative to the unembedded method, with a mean unsigned error of 0.07 eV and a standard deviation of ∼0.1 eV, in exchange for accelerating the calculations by many orders of magnitude. By employing embedded EOM-CC methods, we computed the core ionization energies of the uracil hexamer, doped fullerene, and chlorophyll molecule, utilizing up to ∼4000 basis functions within 1 eV from experimental values. Such calculations are not currently possible with the unembedded EOM-CC method.

Curvature perturbations from preheating with scale dependence

We extend the formalism to calculate non-Gaussianity of primordial curvature perturbations produced by preheating in the presence of a light scalar field. The calculation is carried out in the separate universe approximation using the non-perturbative delta N formalism and lattice field theory simulations. Initial conditions for simulations are drawn from a statistical ensemble determined by modes that left the horizon during inflation, with the time-dependence of Hubble rate during inflation taken into account. Our results show that cosmic variance, i.e., the contribution from modes with wavelength longer than the size of the observable universe today, plays a key role in determining the dominant contribution. We illustrate our formalism by applying it to an observationally-viable preheating model motivated by non-minimal coupling to gravity, and study its full parameter dependence.

Efficient and Accurate Separable Models for Discretized Material Optimization: A Continuous Perspective Based on Topological Derivatives

Multi-material design optimization problems can, after discretization, be solved by the iterative solution of simpler sub-problems which approximate the original problem at an expansion point to first order. In particular, models constructed from convex separable first order approximations have a long and successful tradition in the design optimization community and have led to powerful optimization tools like the prominently used method of moving asymptotes (MMA). In this paper, we introduce several new separable approximations to a model problem and examine them in terms of accuracy and fast evaluation. The models can, in general, be nonconvex and are based on the Sherman–Morrison–Woodbury matrix identity on the one hand, and on the mathematical concept of topological derivatives on the other hand. We show a surprising relation between two models originating from these two—at a first sight—very different concepts. Numerical experiments show a high level of accuracy for two of our proposed models while also their evaluation can be performed efficiently once enough data has been precomputed in an offline stage. Additionally it is demonstrated that suboptimal decisions can be avoided using our most accurate models.

Plane crack problems within strain gradient elasticity and mixed finite element implementation

An alternative approach is proposed and applied to solve boundary value problems within the strain gradient elasticity theory. A mixed variation formulation of the finite element method (FEM) based on the concept of the Galerkin method is used. To construct finite-dimensional subspaces separate approximations of displacements, deformations, stresses, and their gradients are implemented by choosing the different sets of piecewise polynomial basis functions, interrelated by the stability condition of the mixed FEM approximation. This significantly simplifies the pre-requirement for approximating functions to belong to class C1 and allows one to use the simplest triangular finite elements with a linear approximation of displacements under uniform or near-uniform triangulation conditions. Global unknowns in a discrete problem are nodal displacements, while the strains and stresses and their gradients are treated as local unknowns. The conditions of existence, uniqueness, and continuous dependence of the solution on the problem’s initial data are formulated for discrete equations of mixed FEM. These are solved by a modified iteration procedure, where the global stiffness matrix for classical elasticity problems is treated as a preconditioning matrix with fictitious elastic moduli. This avoids the need to form a global stiffness matrix for the problem of strain gradient elasticity since it is enough to calculate only the residual vector in the current approximation. A set of modeling plane crack problems is solved. The obtained solutions agree with the results available in the relevant literature. Good convergence is achieved by refining the mesh for all scale parameters. All three problems under study exhibit specific qualitative features characterizing strain gradient solutions namely crack stiffness increase with length scale parameter and cusp-like closure effect.

GUGA-based MRCI approach with core-valence separation approximation (CVS) for the calculation of the core-excited states of molecules.

We develop and demonstrate how to use the Graphical Unitary Group Approach (GUGA)-based MRCISD with Core-Valence Separation (CVS) approximation to compute the core-excited states. First, perform a normal Self-Consistent-Field (SCF) or valence MCSCF calculation to optimize the molecular orbitals. Second, rotate the optimized target core orbitals and append to the active space, form an extended CVS active space, and perform a CVS-MCSCF calculation for core-excited states. Finally, construct the CVS-MRCISD expansion space and perform a CVS-MRCISD calculation to optimize the CI coefficients based on the variational method. The CVS approximation with GUGA-based methods can be implemented by flexible truncation of the Distinct Row Table. Eliminating the valence-excited configurations from the CVS-MRCISD expansion space can prevent variational collapse in the Davidson iteration diagonalization. The accuracy of the CVS-MRCISD scheme was investigated for excitation energies and compared with that of the CVS-MCSCF and CVS-CASPT2 methods using the same active space. The results show that CVS-MRCISD is capable of reproducing well-matched vertical core excitation energies that are consistent with experiments by combining large basis sets and a rational reference space. The calculation results also highlight the fact that the dynamic correlation between electrons makes an undeniable contribution in core-excited states.

Strict separation and numerical approximation for a non–local Cahn–Hilliard equation with single–well potential

Strict separation and numerical approximation for a non–local Cahn–Hilliard equation with single–well potential

Study of optical properties of DM–DM planar interface by incorporating non-linearity and NID space

Study of the optical characteristics of materials, objects and geometries has wider role and applications in science and engineering. Reflection and transmission coefficients are used to study the optical properties of planar geometries. Primary aim of the presented work is to study the reflection and transmission of second harmonic generation in non-integer dimensional environment. Nonlinear medium in our considered geometry is of second harmonic generation type hence we only studied the second order reflection and transmission characteristics. Solution of the nonlinear wave equation is obtained by using slowly varying amplitude approximation and method of separation of variables in NID space is used to study how the presence of NID medium alter the electromagnetic waves. As a special case of the original geometry we also studied the changes in the behavior of the coefficients when an epsilon negative and a mu negative NID mediums are used as a reflected half space. In all the cases impact of the non-linearity and the noninteger dimensions on the unknown coefficients are studied separately. It is studied that higher amplitude of the reflection coefficient can be achieved by using a dielectric magnetic NID medium compared to epsilon negative NID medium. On the other hand it is also noted that for epsilon near zero medium, amplitude of the reflection coefficient reaches zero for specific values of the nonlinear permeability and incident angle whereas, for mu negative NID medium amplitude of both the coefficients increases (decreases) by increasing the values of ϵic(ϵrc). It is also noted that dimensions of the NID mediums can be used as a controlling factor for the amplitude of the coefficients by keeping the same shape. For the verification of the analytical results nonlinear power law is used.

Unraveling the variational breakdown of core valence separation calculations: Diagnostic and cure to the over relaxation error of double core hole states.

The core valence separation (CVS) approximation is the most employed strategy to prevent the variational collapse of standard wave function optimization when attempting to compute electronic states bearing one or more electronic vacancies in core orbitals. Here, we explore the spurious consequences of this approximation on the properties of the computed core hole states. We especially focus on the less studied case of double core hole (DCH) states, whose spectroscopic interest has recently been rapidly growing. We show that the CVS error leads to a systematic underestimation of DCH energies, a property in stark contrast with the case of single core hole states. We highlight that the CVS error can then be interpreted as an over relaxation effect and design a new correction strategy adapted to these specificities.

Coupled Cluster Simulation of Impulsive Stimulated X-ray Raman Scattering.

Time-dependent equation-of-motion coupled cluster (TD-EOM-CC) is used to simulate impulsive stimulated X-ray Raman scattering (ISXRS) of ultrashort laser pulses by neon, carbon monoxide, pyrrole, and p-aminophenol. The TD-EOM-CC equations are expressed in the basis of field-free EOM-CC states, where the calculation of the core-excited states is simplified through the use of the core-valence separation (CVS) approximation. The transfer of electronic population from the ground state to the core- and valence-excited states is calculated for different numbers of included core- and valence-excited states, as well as for electric field pulses with different polarizations and carrier frequencies. The results indicate that Gaussian pulses can transfer significant electronic populations to the valence states through the Raman process. The sensitivity of this population transfer to the model parameters is analyzed. The time-dependent electronic density for p-aminophenol is also showcased, supporting the interpretation that ISXRS involves localized core excitations and can be used to rapidly generate valence wavepackets.

Time-Dependent Density Functional Theory for X-ray Absorption Spectra: Comparing the Real-Time Approach to Linear Response.

We simulate X-ray absorption spectra at elemental K-edges using time-dependent density functional theory (TDDFT) in both its conventional linear-response implementation and its explicitly time-dependent or "real-time" formulation. Real-time TDDFT simulations enable broadband spectra calculations without the need to invoke frozen occupied orbitals ("core/valence separation"), but we find that these spectra are often contaminated by transitions to the continuum that originate from lower-energy core and semicore orbitals. This problem becomes acute in triple-ζ basis sets, although it is sometimes sidestepped in double-ζ basis sets. Transitions to the continuum acquire surprisingly large dipole oscillator strengths, leading to spectra that are difficult to interpret. Meaningful spectra can be recovered by means of a filtering technique that decomposes the spectrum into contributions from individual occupied orbitals, and the same procedure can be used to separate L- and K-edge spectra arising from different elements within a given molecule. In contrast, conventional linear-response TDDFT requires core/valence separation but is free of these artifacts. It is also significantly more efficient than the real-time approach, even when hundreds of individual states are needed to reproduce near-edge absorption features and even when Padé approximants are used to reduce the real-time simulations to just 2-4 fs of time propagation. Despite the cost, the real-time approach may be useful to examine the validity of the core/valence separation approximation.

Multi-field inflation with large scalar fluctuations: non-Gaussianity and perturbativity

Recently multi-field inflation models that can produce large scalar fluctuations on small scales have drawn a lot of attention, primarily because they could lead to primordial black hole production and generation of large second-order gravitational waves. In this work, we focus on models where the scalar fields responsible for inflation live on a hyperbolic field space. In this case, geometrical destabilisation and non-geodesic motion are responsible for the peak in the scalar power spectrum. We present new results for scalar non-Gaussianity and discuss its dependence on the model's parameters. On scales around the peak, we typically find that the non-Gaussianity is large and close to local in form. We validate our results by employing two different numerical techniques, utilising the transport approach, based on full cosmological perturbation theory, and the δN formalism, based on the separate universe approximation. We discuss implications of our results for the perturbativity of the underlying theory, focusing in particular on versions of these models with potentially relevant phenomenology at interferometer scales.

Structure-preserving model reduction for port-Hamiltonian systems based on separable nonlinear approximation ansatzes

We discuss structure-preserving model order reduction for port-Hamiltonian systems based on a nonlinear approximation ansatz which is linear with respect to a part of the state variables of the reduced-order model. In recent years, such nonlinear approximation ansatzes have gained more and more attention especially due to their effectiveness in the context of model reduction for transport-dominated systems which are challenging for classical linear model reduction techniques. We demonstrate that port-Hamiltonian reduced-order models can often be obtained by a residual minimization approach where a suitable weighted norm is used for the residual. Moreover, we discuss sufficient conditions for the resulting reduced-order models to be stable. Finally, the methodology is illustrated by means of two transport-dominated numerical test cases, where the ansatz functions are determined based on snapshot data of the full-order state.

Spatio-temporal non-localities in a solar-like mean-field dynamo

ABSTRACT The scale separation approximation, which is in the base of the solar mean-field dynamo models, can be hardly justified both by observations and theoretical applications to astrophysical dynamos. The general expression for the mean turbulent electromotive force can be written in integral form with convolution of the turbulent effects and mean magnetic field variations over scales of the turbulent flows and global scales of the mean-field dynamo. Following results of direct numerical simulations (DNS), which had been reported earlier, we take the Lorentzian form of the integral convolution kernels as an experimental fact. It allows us to approximate the governing equation for the mean electromotive force by the reaction–diffusion type equation. Solution of the eigenvalue problem reveals a few curious properties of the dynamo model with the non-local mean electromotive force. We find a decrease of the critical dynamo instability threshold, and an increase the dynamo periods of the unstable modes, as reported in earlier studies. Simultaneously, the non-local model shows substantially lower growth rate of the unstable dynamo modes in proximity of the critical threshold than the model which employs the scale separation approximation. We verify these findings using the non-linear solar dynamo model. For the supercritical regime, when the α-effect magnitude is about twice of the instability threshold, the model shows the Parker’s dynamo wave solutions with the wave propagating from the mid-latitude at the bottom of the convection zone towards the solar equator at the surface.

Development and verification of a Monte Carlo two-step method for lead-based fast reactor neutronics analysis

With the rise of economic and safety standards for nuclear reactors, new concepts of Gen-IV reactors and modular reactors showed more complex designs that challenge current tools for reactor physics analysis. A Monte Carlo (MC) two-step method was proposed in this work. This calculation scheme uses the continuous-energy MC method to generate multi-group cross-sections from heterogeneous models. The multi-group MC method, which can adapt locally-heterogeneous models, is used in the core calculation step. This calculation scheme is verified using a Gen-IV modular lead-based fast reactor (LFR) benchmark case. The influence of homogenized patterns, scatter approximations, flux separable approximation, and local heterogeneity in core calculation on simulation results are investigated. Results showed that the cross-sections generated using the 3D assembly model with a locally heterogeneous representation of control rods lead to an accurate estimation with less than 270 pcm bias in core reactivity, 0.5% bias in control rod worth, and 1.5% bias on power distribution. The study verified the applicability of multi-group cross-sections generated with the MC method for LFR analysis. The study also proved the feasibility of multi-group MC in core calculation with local heterogeneity, which saves 85% time compared to the continuous-energy MC.

Double-Hybrid Density Functional Theory for Core Excitations: Theory and Benchmark Calculations.

The double-hybrid (DH) time-dependent density functional theory is extended to core excitations. Two different DH formalisms are presented utilizing the core-valence separation (CVS) approximation. First, a CVS-DH variant is introduced relying on the genuine perturbative second-order correction, while an iterative analogue is also presented using our second-order algebraic-diagrammatic construction [ADC(2)]-based DH ansatz. The performance of the new approaches is tested for the most popular DH functionals using the recently proposed XABOOM [J. Chem. Theory Comput.2021, 17, 1618] benchmark set. In order to make a careful comparison, the accuracy and precision of the methods are also inspected. Our results show that the genuine approaches are highly competitive with the more advanced CVS-ADC(2)-based methods if only excitation energies are required. In contrast, as expected, significant differences are observed in oscillator strengths; however, the precision is acceptable for the genuine functionals as well. Concerning the performance of the CVS-DH approaches, the PBE0-2/CVS-ADC(2) functional is superior, while its spin-opposite-scaled variant is also recommended as a cost-effective alternative. For these approaches, significant improvements are realized in the error measures compared with the popular CVS-ADC(2) method.