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In this contribution, we present the implementation of a second-order CASSCF algorithm in conjunction with the Cholesky decomposition of the two-electron repulsion integrals. The algorithm, called Norm-Extended Optimization, guarantees…

Chemical Physics · Physics 2021-04-09 Tommaso Nottoli , Jürgen Gauss , Filippo Lipparini

Efficient performance of a number of engineering systems is achieved through different modes of operation - yielding systems described as "hybrid", containing both real-valued and discrete decision variables. Prominent examples of such…

Optimization and Control · Mathematics 2019-10-22 Ehsan Taheri , John L. Junkins , Ilya Kolmanovsky , Anouck Girard

Selected configuration interaction (SCI) methods are currently enjoying a resurgence due to several recent developments which improve either the overall computational efficiency or the compactness of the resulting SCI vector. These recent…

Strongly Correlated Electrons · Physics 2020-12-18 Vibin Abraham , Nicholas J. Mayhall

We present a new, non-variational orbital-optimization scheme for the Antisymmetric Product of one-reference orbital Geminal wave function. Our approach is motivated by the observation that an orbital-optimized seniority-zero configuration…

A successful and commonly used ab initio method for the calculation of crystal field levels and magnetic anisotropy of lanthanide complexes consists of spin-adapted state-averaged CASSCF calculations followed by state interaction with…

Chemical Physics · Physics 2016-06-08 Willem Van den Heuvel , Simone Calvello , Alessandro Soncini

We propose a state-averaged orbital optimization scheme for improving the accuracy of excited states of the electronic structure Hamiltonian for use on near-term quantum computers. Instead of parameterizing the orbital rotation operator in…

Chemical Physics · Physics 2024-04-09 Joel Bierman , Yingzhou Li , Jianfeng Lu

Even when starting with a very poor initial guess, the iterative configuration interaction (iCI) approach can converge from above to full CI very quickly by constructing and diagonalizing a small Hamiltonian matrix at each…

Chemical Physics · Physics 2020-01-07 Ning Zhang , Wenjian Liu , Mark R. Hoffmann

The interplay between advances in stochastic and deterministic algorithms has recently led to development of interesting new selected configuration interaction (SCI) methods for solving the many body Schr\"{o}dinger equation. The…

Strongly Correlated Electrons · Physics 2018-08-08 Norm M. Tubman , Daniel S. Levine , Diptarka Hait , Martin Head-Gordon , K. Birgitta Whaley

This work presents the formalism for evaluating molecular SCF equations, as adapted to four$-$component Dirac spinors, which in turn reduce to Slater$-$type orbitals with non$-$integer principal quantum numbers in the non$-$relativistic…

Chemical Physics · Physics 2019-12-10 A. Bagci

We present a combination of the bi-orthogonal orbital optimisation framework with the recently introduced xTC version of transcorrelation. This allows us to implement non-iterative perturbation based methods on top of the transcorrelated…

Chemical Physics · Physics 2024-04-12 Daniel Kats , Evelin M. C. Christlmaier , Thomas Schraivogel , Ali Alavi

We introduce an algorithm that can be used to perform stochastic perturbation theory (sPT) to correct any non-linearly parametrized wavefunction that can be optimized using orbital space Variational Monte Carlo (VMC). Although the…

Strongly Correlated Electrons · Physics 2018-03-13 Sandeep Sharma

In this work we present a multi-orbital form of the Two-Particle Self-Consistent approach (TPSC), here the effective local and static irreducible interaction vertices are determined by means of the Dynamical Mean-Field Theory (DMFT). This…

Strongly Correlated Electrons · Physics 2023-06-16 Karim Zantout , Steffen Backes , Aleksandar Razpopov , Dominik Lessnich , Roser Valenti

In this work we demonstrate how to compute the one- and two-body reduced density matrices within the spin-adapted full configuration interaction quantum Monte Carlo (FCIQMC) method, which is based on the graphical unitary group approach…

Chemical Physics · Physics 2021-09-27 Werner Dobrautz , Oskar Weser , Nikolay Bogdanov , Ali Alavi , Giovanni Li Manni

Selected configuration interaction (sCI) methods including second-order perturbative corrections provide near full CI (FCI) quality energies with only a small fraction of the determinants of the FCI space. Here, we introduce both a…

Chemical Physics · Physics 2018-08-09 Yann Garniron , Anthony Scemama , Emmanuel Giner , Michel Caffarel , Pierre-François Loos

Recent advances in selected CI, including the adaptive sampling configuration interaction (ASCI) algorithm and its heat bath extension, have made the ASCI approach competitive with the most accurate techniques available, and hence an…

It has been well established that the Jastrow correlation factor can effectively capture the electron correlation effects, and thus, the efficient optimization of the many-body wave function including the Jastrow correlation factor is of…

Atomic Physics · Physics 2023-09-12 Masayuki Ochi

In this work, we develop a mathematical framework for a Selected Configuration Interaction (SCI) algorithm within a bi-orthogonal basis for transcorrelated (TC) calculations. The bi-orthogonal basis used here serves as the equivalent of the…

Chemical Physics · Physics 2023-06-22 Abdallah Ammar , Anthony Scemama , Emmanuel Giner

We present a fully variational locally scaled self-interaction corrected (SIC) energy functional using complex optimal orbitals. This represents an important milestone for fully variational SIC energy functionals, which have been shown to…

Using the complete orthonormal sets of radial parts of nonrelativitistic exponential type orbitals (2,1, 0, 1, 2, ...) and spinor type tensor spherical harmonics of rank s the new formulae for the 2(2s+1)-component relativistic spinors…

Mathematical Physics · Physics 2015-03-13 I. I. Guseinov

We present a quantum linear response (qLR) approach within an active-space framework for computing indirect nuclear spin-spin coupling constants, a key ingredient in NMR spectra predictions. The method employs the unitary coupled cluster…