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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Benchmarking an Embedded Adaptive Sampling Configuration Interaction Method for Surface Reactions: H 2 Desorption from and CH 4 Dissociation on Cu(111)

Embedded (emb-) correlated wavefunction (CW) theory enables accurate assessments of both ground- and excited-state reaction mechanisms involved in heterogeneous catalysis. Embedded multireference second-order perturbation theory (emb-MRPT2) based on reference wavefunctions generated via embedded complete active space self-consistent field (emb-CASSCF) theory is currently state-of-the-art. However, the factorial scaling of CASSCF limits the size of active space and the complexity of systems that can be studied. In this work, we assess the efficacy of an alternative CW method, adaptive sampling configuration interaction (ASCI)–which enables large active spaces to be used–for studying surface reactions. We couple ASCI with density functional embedding theory (DFET) and benchmark its performance for two reactions: H 2 desorption from and CH 4 dissociation on the Cu(111) surface. Unlike embedded complete active space second-order perturbation theory (emb-CASPT2) that accurately reproduces a measured H 2 desorption barrier, embedded ASCI, using a very large active space (though one that still comprises a small portion of the full set of orbitals) fails to do so. Adding an extra correlation term from embedded Møller–Plesset second-order perturbation theory (emb-MP2) improves the desorption barrier and endothermicity predictions. Thus, the inaccuracy of embedded ASCI comes from the missing dynamic correlation from the many other electrons and orbitals not included in the active space. For CH 4 dissociation, again embedded ASCI overestimates the dissociation barrier compared to emb-CASPT2 predictions. Adding dynamic correlation from emb-MP2 helps correct the barrier. However, this composite approach suffers from double counting of correlation within embedded ASCI followed by emb-MP2 calculations. We therefore conclude that the state-of-the-art emb-MRPT2 based on reference wavefunctions generated via emb-CASSCF remains the method of choice for studying surface reactions. emb-ASCI is useful when large active spaces beyond the limit of emb-CASSCF are essential, such as to study complex surface reactions with significant multiconfigurational character (static correlation) but weak dynamic correlation.

08 HYDROGEN↗
DOE OSTI2019

Dynamical mean field theory simulations with the adaptive sampling configuration interaction method

In the pursuit of accurate descriptions of strongly correlated quantum many-body systems, dynamical mean field theory (DMFT) has been an invaluable tool for elucidating the spectral properties and quantum phases of both phenomenological models and ab initio descriptions of real materials. Key to the DMFT process is the self-consistent map of the original system into an Anderson impurity model, the ground state of which is computed using an impurity solver. The power of the method is thus limited by the complexity of the impurity model the solver can handle. Simulating realistic systems generally requires many correlated sites. By adapting the recently proposed adaptive sampling configuration interaction (ASCI) method as an impurity solver, we enable much more efficient zero-temperature DMFT simulations. The key feature of the ASCI method is that it selects only the most relevant Hilbert space degrees of freedom to describe the ground state. This reduces the numerical complexity of the calculation, which will allow us to pursue future DMFT simulations with more correlated impurity sites than in previous works. Here, we present the ASCI-DMFT method and example calculations on the one- and two-dimensional Hubbard models that exemplify its efficient convergence and timing properties. We show that the ASCI approach is several orders of magnitude faster than the current best published ground-state DMFT simulations, which allows us to study the bath discretization error in simulations with small clusters, as well as to address cluster sizes beyond the current state of the art. Finally, our approach can also be adapted for other embedding methods such as density matrix embedding theory and self-energy embedding theory.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Tailoring light-induced charge transfer and intersystem crossing in FeCO using time-dependent spin–orbit configuration interaction

Real-time (RT) electronic structure methods provide a natural framework for describing light–matter interactions in arbitrary time-dependent electromagnetic fields (EMF). Optically induced excited state transitions are of particular interest, which require tuned EMF to drive population transfer to and from the specific state(s) of interest. Intersystem crossing, or spin-flip, may be driven through shaped EMF or laser pulses. These transitions can result in long-lived “spin-trapped” excited states, which are especially useful for materials requiring charge separation or protracted excited state lifetimes. Time-dependent configuration interaction (TDCI) is unique among RT methods in that it may be implemented in a basis of eigenstates, allowing for rapid propagation of the time-dependent Schrödinger equation. The recent spin–orbit TDCI (TD-SOCI) enables a real-time description of spin-flip dynamics in an arbitrary EMF and, therefore, provides an ideal framework for rational pulse design. The present study explores the mechanism of multiple spin-flip pathways for a model transition metal complex, FeCO, using shaped pulses designed to drive controlled intersystem crossing and charge transfer. These results show that extremely tunable excited state dynamics can be achieved by considering the dipole transition matrix elements between the states of interest.

Chemistry↗
DOE OSTI2016

Resolution-of-identity stochastic time-dependent configuration interaction for dissipative electron dynamics in strong fields

In this contribution, we introduce a method for simulating dissipative, ultrafast many-electron dynamics in intense laser fields. The method is based on the norm-conserving stochastic unraveling of the dissipative Liouville-von Neumann equation in its Lindblad form. The N-electron wave functions sampling the density matrix are represented in the basis of singly excited configuration state functions. The interaction with an external laser field is treated variationally and the response of the electronic density is included to all orders in this basis. The coupling to an external environment is included via relaxation operators inducing transition between the configuration state functions. Single electron ionization is represented by irreversible transition operators from the ionizing states to an auxiliary continuum state. The method finds its efficiency in the representation of the operators in the interaction picture, where the resolution-of-identity is used to reduce the size of the Hamiltonian eigenstate basis. The zeroth-order eigenstates can be obtained either at the configuration interaction singles level or from a time-dependent density functional theory reference calculation. The latter offers an alternative to explicitly time-dependent density functional theory which has the advantage of remaining strictly valid for strong field excitations while improving the description of the correlation as compared to configuration interaction singles. The method is tested on a well-characterized toy system, the excitation of the low-lying charge transfer state in LiCN.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

The ionic states of iodobenzene studied by photoionization and ab initio configuration interaction and DFT computations

New valence electron photoelectron spectra of iodobenzene obtained using synchrotron radiation have been recorded. Ionization energies (IEs) determined using multi-configuration SCF calculation (MCSCF) procedures confirmed the adiabatic IE order as: X{sup 2}B{sub 1}<A{sup 2}A{sub 2}<B{sup 2}B{sub 2}<C{sup 2}B{sub 1}. Although it is convenient to retain C{sub 2v} labelling, there is an evidence that minor distortion to C{sub S} symmetry occurs at the MCSCF level for the C state. The fifth ionization process shown to be D{sup 2}A{sub 1} exhibits dissociation to C{sub 6}H{sub 5}{sup +} + I both in the experimental and theoretical studies. The calculated Franck-Condon vibrational spectral envelopes, including hot band contributions, for the first four ionic states reproduce the observed peak positions and intensities with reasonable accuracy. In order to simulate the observed spectra, different bandwidths are required for different states. The increase in the required bandwidths for the A{sup 2}A{sub 2} and B{sup 2}B{sub 2} states is attributed to internal conversion to lower-lying states. The presence of relatively high intensity sequence bands leads to asymmetry of each of the X{sup 2}B{sub 1} state bands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Investigation of the multiplet features of SrTiO 3 in X-ray absorption spectra based on configuration interaction calculations

Synchrotron-based L 2,3 -edge absorption spectra show strong sensitivities to the local electronic structure and chemical environment. However, detailed physical information cannot be extracted easily without computational aids. Here in this study using the experimental Ti L 2,3 -edges absorption spectrum of SrTiO 3 as a fingerprint and considering full multiplet effects, calculations yield different energy parameters characterizing local ground state properties. The peak splitting and intensity ratios of the L 3 and L 2 set of peaks are carefully analyzed quantitatively, giving rise to a small hybridization energy around 1.2 eV, and the different hybridization energy values reported in the literature are further addressed. Finally, absorption spectra with different linearly polarized photons under various tetragonal crystal fields are investigated, revealing a non-linear orbital–lattice interaction, and a theoretical guidance for material engineering of SrTiO 3 -based thin films and heterostructures is offered. Finally, detailed analysis of spectrum shifts with different tetragonal crystal fields suggests that the e g crystal field splitting is a necessary parameter for a thorough analysis of the spectra, even though it is not relevant for the ground state properties.

3 d transition metal oxide↗
DOE OSTI2023

Hybrid eigensolvers for nuclear configuration interaction calculations

We examine and compare several iterative methods for solving large-scale eigenvalue problems arising from nuclear structure calculations. In particular, we discuss the possibility of using block Lanczos method, a Chebyshev filtering based subspace iterations and the residual minimization method accelerated by direct inversion of iterative subspace (RMM-DIIS) and describe how these algorithms compare with the standard Lanczos algorithm and the locally optimal block preconditioned conjugate gradient (LOBPCG) algorithm. Although the RMM-DIIS method does not exhibit rapid convergence when the initial approximations to the desired eigenvectors are not sufficiently accurate, it can be effectively combined with either the block Lanczos or the LOBPCG method to yield a hybrid eigensolver that has several desirable properties. We will describe a few practical issues that need to be addressed to make the hybrid solver efficient and robust.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2023

Schematic model for induced fission in a configuration-interaction approach

We model fission at barrier-top energies in a simplified model space that permits comparison of different components of the residual nucleon-nucleon interaction. The model space is built on particle-hole excitations of reference configurations. These are Slater determinants of uniformly spaced orbitals characterized only by their quantum numbers and orbital energies. The residual interaction in the Hamiltonian includes the diabatic interaction connecting similar orbitals at different deformations, the pairing interaction between like nucleons, and a schematic off-diagonal neutron-proton interaction. We find that the fission reaction probability is sensitive to the off-diagonal neutron-proton interaction much more than to the pairing and the diabatic interactions. In particular, the transmission coefficients become insensitive to the strength of the pairing interaction when the neutron-proton interaction is large. Here, we also find that the branching ratio is insensitive to the final-state scission dynamics, as is assumed in the well-known Bohr-Wheeler theory.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2026

Low-Lying Excited States of Linear All- Trans Polyenes: Insights from Analytic Gradient and Nonadiabatic Coupling Calculations Based on Multireference Configuration Interaction

Polyenes serve as a rigorous test for theoretical models and electronic structure methods, playing a key role in advancing computational and theoretical chemistry. Here, we present a high-level theoretical investigation of linear, all-trans polyenes using energy gradients and nonadiabatic coupling vectors based on an MR-CISD wave function to describe electronic transitions involving the ground state (1 1 A g – ) and three low-lying excited states (2 1 A g – , 1 1 B u + , and 2 1 B u – ) of hexatriene, octatetraene, and decapentaene. This approach enables accurate evaluation of both adiabatic and vertical excitation and emission energies, yielding results in excellent agreement with experiment, as well as locating minima on the crossing seam between adiabatic states. Our results show that vertical excitation energies to the 1 1 B u + state are blue-shifted by 0.2–0.3 eV relative to the experimental absorption maximum, whereas the vertical emission energy from the 2 1 A g – state is red-shifted by ∼0.2 eV relative to the experimental emission maximum. Upon relaxation from the Franck–Condon geometry, the 2 1 A g – state stabilizes by around 1 eV, compared to 0.2–0.3 eV for the 1 1 B u + state. An analysis of the S 1 /S 0 crossing seam in hexatriene shows that its minimum involves asymmetric backbone deformations and provides an efficient channel for ultrafast internal conversion to the ground state, consistent with the absence of detectable fluorescence in this molecule. These results demonstrate the power of analytic gradients and nonadiabatic coupling vectors based on an MR-CISD wave function for accurately characterizing the electronic structure and photophysics of polyenes.

Excited states↗