Second-Order Multi-Reference Algebraic Diagrammatic Construction Theory for Photoelectron Spectra of Strongly Correlated Systems

Abstract

We present a second-order formulation of multi-reference algebraic diagrammatic construction theory [Sokolov, A. Yu. J. Chem. Phys. 2018, 149, 204113] for simulating photoelectron spectra of strongly correlated systems (MR-ADC(2)). The MR-ADC(2) method uses second-order multi-reference perturbation theory (MRPT2) to efficiently obtain ionization energies and intensities for many photoelectron transitions in a single computation. In contrast to conventional MRPT2 methods, MR-ADC(2) provides information about ionization of electrons in all orbitals (i.e., core and active) and allows to compute transition intensities in straightforward and efficient way. Although equations of MR-ADC(2) depend on four-particle reduced density matrices, we demonstrate that computation of these large matrices can be completely avoided without introducing any approximations. The resulting MR-ADC(2) implementation has a lower computational scaling compared to conventional MRPT2 methods. We present results of MR-ADC(2) for photoelectron spectra of small molecules, carbon dimer, and equally-spaced hydrogen chains (H10 and H30) and outline directions for future developments.

References in corpus (28)

• Electronic Structure Calculations with Dynamical Mean-Field Theory: A Spectral Density Functional Approach
• Quasiparticle Self-Consistent GW Theory
• All-electron self-consistent GW approximation: Application to Si, MnO, and NiO
• Ab Initio Quantum Chemistry using the Density Matrix Renormalization Group
• Heat-bath Configuration Interaction: An efficient selected CI algorithm inspired by heat-bath sampling
• Semistochastic Heat-bath Configuration Interaction method: selected configuration interaction with semistochastic perturbation theory
• The density matrix renormalization group for ab initio quantum chemistry
• Towards the solution of the many-electron problem in real materials: equation of state of the hydrogen chain with state-of-the-art many-body methods
• CheMPS2: a free open-source spin-adapted implementation of the density matrix renormalization group for ab initio quantum chemistry
• N-electron valence state perturbation theory based on a density matrix renormalization group reference function, with applications to the chromium dimer and poly-p-phenylene vinylene oligomer
• Excited states using semistochastic heat-bath configuration interaction
• A canonical transformation theory from extended normal ordering
• Multi-reference perturbation theory with Cholesky decomposition for the density matrix renormalization group
• The description of strong correlation within self-consistent Green's function second-order perturbation theory
• Automatic code generation enables nuclear gradient computations for fully internally contracted multireference theory
• Towards ab initio self-energy embedding theory in quantum chemistry
• Strong electronic correlation in the Hydrogen chain: a variational Monte Carlo study
• Strong correlations via constrained-pairing mean-field theory
• Second-order Green's function perturbation theory for periodic systems
• Time-step targeting time-dependent and dynamical density matrix renormalization group algorithms with ab initio Hamiltonians
• DMRG-CASPT2 study of the longitudinal static second hyperpolarizability of all-trans polyenes
• Dynamical Mean-Field Theory for Quantum Chemistry
• Self-energy embedding theory (SEET) for periodic systems
• A time-dependent formulation of multi-reference perturbation theory
• Time-dependent N-electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes
• Multi-reference algebraic diagrammatic construction theory for excited states: General formulation and first-order implementation
• Towards numerically robust multireference theories: The driven similarity renormalization group truncated to one- and two-body operators
• Block product density matrix embedding theory for strongly correlated spin systems

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• Multireference Algebraic Diagrammatic Construction Theory for Excited States: Extended Second-Order Implementation and Benchmark
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• Algebraic Diagrammatic Construction Theory for Simulating Charged Excited States and Photoelectron Spectra
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• Simulating Transient X-ray Photoelectron Spectra of Fe(CO)5 and Its Photodissociation Products With Multireference Algebraic Diagrammatic Construction Theory
• Quantifying and reducing spin contamination in algebraic diagrammatic construction theory of charged excitations
• Algebraic Diagrammatic Construction Theory of Charged Excitations With Consistent Treatment of Spin-Orbit Coupling and Dynamic Correlation
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