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The general procedure underlying Hartree-Fock and Kohn-Sham density functional theory calculations consists in optimizing orbitals for a self-consistent solution of the Roothaan-Hall equations in an iterative process. It is often ignored…

Chemical Physics · Physics 2017-03-16 Alain C. Vaucher , Markus Reiher

In a recent work, we introduced the foundations of an orthogonally constrained complete active space self-consistent field (OC-CASSCF) framework that produces state-specific molecular orbitals for mutually orthogonal multiconfigurational…

Chemical Physics · Physics 2026-01-28 Loris Delafosse , Vincent Robert , Saad Yalouz

Orbital optimization procedure is widely called in electronic structure simulation. To efficiently find the orbital optimization solution, we developed a new second order orbital optimization algorithm, co-iteration augmented Hessian (CIAH)…

Chemical Physics · Physics 2017-01-11 Qiming Sun

It has recently been shown that configuration state functions (CSF) with local orbitals can provide a compact reference state for low-spin open-shell electronic structures, such as antiferromagnetic states. However, optimizing a low-spin…

Chemical Physics · Physics 2025-08-05 Hugh G. A. Burton

The convergence property of a stochastic algorithm for the self-consistent field (SCF) calculations of electron structures is studied. The algorithm is formulated by rewriting the electron charges as a trace/diagonal of a matrix function,…

Numerical Analysis · Mathematics 2023-04-20 Taehee Ko , Xiantao Li

We extend the standard notion of self-concordance to non-convex optimization and develop a family of second-order algorithms with global convergence guarantees. In particular, two function classes -- \textit{weakly self-concordant}…

Optimization and Control · Mathematics 2026-04-07 Donald Goldfarb , Lexiao Lai , Tianyi Lin , Jiayu Zhang

We describe a version of an algorithm for evolving self-gravitating collections of particles that should be nearly ideal for parallel architectures. Our method is derived from the ``self-consistent field'' (SCF) approach suggested…

Astrophysics · Physics 2016-08-30 Lars Hernquist , Steinn Sigurdsson , Greg L. Bryan

Electronic structure calculations, such as in the Hartree-Fock or Kohn-Sham density functional approach, require an initial guess for the molecular orbitals. The quality of the initial guess has a significant impact on the speed of…

Chemical Physics · Physics 2019-03-13 Susi Lehtola

We present a self consistent field approach (SCF) within the Adaptive Derivative-Assembled Problem-Tailored Ansatz Variational Quantum Eigensolver (ADAPT-VQE) framework for efficient quantum simulations of chemical systems on near-term…

In this work, we present a one-step second-order converger for state-specific (SS) and state-averaged (SA) complete active space self-consistent field (CASSCF) wave functions. Robust convergence is achieved through step restrictions using a…

Chemical Physics · Physics 2022-06-08 Benjamin Helmich-Paris

We present an efficient quasi-Newton orbital solver optimized to reduce the number of gradient (Fock matrix) evaluations. The solver optimizes orthogonal orbitals by sequences of unitary rotations generated by the (preconditioned)…

Chemical Physics · Physics 2023-12-20 Samuel A. Slattery , Kshitijkumar Surjuse , Edward F. Valeev

We report an efficient algorithm using density fitting for the relativistic complete active space self-consistent field (CASSCF) method, which is significantly more stable than the algorithm previously reported by one of the authors [J. E.…

Chemical Physics · Physics 2018-08-01 Ryan D. Reynolds , Takeshi Yanai , Toru Shiozaki

We have developed a couple of optimal damping algorithms (ODAs) for unrestricted Hartree-Fock (UHF) calculations of open-shell molecular systems. A series of equations were derived for both concurrent and alternate constructions of alpha-…

Chemical Physics · Physics 2018-01-25 Jun-ichi Yamamoto , Yuji Mochizuki

This article is concerned with the numerical solution of subspace optimization problems, consisting of minimizing a smooth functional over the set of orthogonal projectors of fixed rank. Such problems are encountered in particular in…

Numerical Analysis · Mathematics 2022-10-17 Eric Cancès , Gaspard Kemlin , Antoine Levitt

In this paper we provide a detailed convergence analysis for fully discrete second order (in both time and space) numerical schemes for nonlocal Allen-Cahn (nAC) and nonlocal Cahn-Hilliard (nCH) equations. The unconditional unique…

Numerical Analysis · Mathematics 2018-02-14 Zhen Guan , John Lowengrub , Cheng Wang

The multiconfiguration self-consistent field (MCSCF) method is revisited with a specific focus on two-electron systems for simplicity. The wave function is represented as a linear combination of Slater determinants. Both the orbitals and…

Chemical Physics · Physics 2026-04-10 Evgueni Dinvay , Rasmus Vikhamar-Sandberg

We present here a review of the fundamental topics of Hartree-Fock theory in Quantum Chemistry. From the molecular Hamiltonian, using and discussing the Born-Oppenheimer approximation, we arrive to the Hartree and Hartree-Fock equations for…

Chemical Physics · Physics 2008-11-25 Pablo Echenique , J. L. Alonso

We present a real-space formulation and higher-order finite-difference implementation of periodic Orbital-free Density Functional Theory (OF-DFT). Specifically, utilizing a local reformulation of the electrostatic and kernel terms, we…

Computational Physics · Physics 2015-12-23 Swarnava Ghosh , Phanish Suryanarayana

An accurate description of electron correlation is one of the most challenging problems in quantum chemistry. The exact electron correlation can be obtained by means of full configuration interaction (FCI). A simple strategy for…

Chemical Physics · Physics 2021-05-14 Jae Woo Park

We present the implementation of a quadratically convergent Self-consistent field (QCSCF) algorithm based on an adaptive trust-radius optimization scheme for restricted open-shell Hartree-Fock (ROHF), restricted Hartree-Fock (RHF), and…

Chemical Physics · Physics 2022-01-12 Tommaso Nottoli , Jürgen Gauss , Filippo Lipparini
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