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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

The variational quantum eigensolver (VQE) is a promising method for simulating molecular systems on near-term quantum computers. This approach employs energy estimation; however, other relevant molecular properties can be extracted from the…

VV10 is a powerful nonlocal density functional for long-range correlation that is used to include dispersion effects in many modern density functionals such as the meta-generalized gradient approximation (mGGA), B97M-V, the hybrid GGA,…

Chemical Physics · Physics 2023-06-07 Jiashu Liang , Xintian Feng , Martin Head-Gordon

We report the derivation and implementation of orbital optimization algorithms for the active space decomposition (ASD) model, which are extensions of complete active space self-consistent field (CASSCF) and its occupation-restricted…

Chemical Physics · Physics 2015-08-17 Inkoo Kim , Shane M. Parker , Toru Shiozaki

We present an efficient orbital optimization procedure that combines the highly GPU accelerated, spin-adapted density matrix renormalization group (DMRG) method with the complete active space self-consistent field (CAS-SCF) approach for…

We present an approximate scheme for analytical gradients and nonadiabatic couplings for calculating state-average density matrix renormalization group self-consistent-field wavefunction. Our formalism follows closely the state-average…

Chemical Physics · Physics 2020-02-18 Leon Freitag , Yingjin Ma , Alberto Baiardi , Stefan Knecht , Markus Reiher

The last several decades have seen significant advances in the theoretical modeling of materials within the fields of solid-state physics and materials science, but many methods commonly applied to this problem struggle to capture strong…

Strongly Correlated Electrons · Physics 2025-04-07 Anna O. Schouten , Simon Ewing , David A. Mazziotti

The calibration of CALPHAD (CALculation of PHAse Diagrams) models involves the solution of a very challenging high-dimensional multiobjective optimization problem. Traditional approaches to parameter fitting predominantly rely on…

Materials Science · Physics 2025-05-06 Courtney Kunselman , Brandon Bocklund , Richard Otis , Raymundo Arroyave

The computation of strongly correlated quantum systems is challenging because of its potentially exponential scaling in the number of electron configurations. Variational calculation of the two-electron reduced density matrix (2-RDM)…

Quantum Physics · Physics 2021-04-01 David A. Mazziotti

We introduce a robust optimization method for flip-free distortion energies used, for example, in parametrization, deformation, and volume correspondence. This method can minimize a variety of distortion energies, such as the symmetric…

Graphics · Computer Science 2022-11-17 Oded Stein , Jiajin Li , Justin Solomon

A new method for implementing the kinetic energy operator for real-space, grid-based electronic structure codes is developed. It is based on multi-order Adaptive Finite Differencing (AFD) and uses atomic pseudo orbitals produced by the…

Computational Physics · Physics 2023-05-23 E. L. Briggs , Wenchang Lu , J. Bernholc

We present the numerical implementation of the time-dependent complete-active-space self-consistent-field (TD-CASSCF) method [Phys. Rev. A, 88, 023402 (2013)] for atoms driven by a strong linearly polarized laser pulse. The present…

Accurate treatment of the long-range electron correlation energy, including van der Waals (vdW) or dispersion interactions, is essential for describing the structure, dynamics, and function of a wide variety of systems. Among the most…

Computational Physics · Physics 2016-05-19 Martin A. Blood-Forsythe , Thomas Markovich , Robert A. DiStasio , Roberto Car , Alán Aspuru-Guzik

Variational minimization of the ground-state energy as a function of the two-electron reduced density matrix (2-RDM), constrained by necessary $N$-representability conditions, provides a polynomial-scaling approach to studying strongly…

Quantum Physics · Physics 2011-11-09 Kasra Naftchi-Ardebili , Nathania W. Hau , David A. Mazziotti

We use the recently-developed Heat-bath Configuration Interaction (HCI) algorithm as an efficient active-space solver to perform multi-configuration self-consistent field calculations (HCISCF) with large active spaces. We give a detailed…

Chemical Physics · Physics 2018-11-08 James E. T. Smith , Adam A. Holmes , Bastien Mussard , Sandeep Sharma

In this work, we present the first derivation and implementation of analytic gradient methods for the computation of the atomic axial tensors (AATs) required for simulations of vibrational circular dichroism (VCD) spectra using…

Chemical Physics · Physics 2025-11-03 Brendan M. Shumberger , T. Daniel Crawford

We develop an energy density matrix that parallels the one-body reduced density matrix (1RDM) for many-body quantum systems. Just as the density matrix gives access to the number density and occupation numbers, the energy density matrix…

Strongly Correlated Electrons · Physics 2015-06-22 Jaron T. Krogel , Jeongnim Kim , Fernando A. Reboredo

We present a Gaussian-basis implementation of orbital-free density-functional theory (OF-DFT) in which the trust-region image method (TRIM) is used for optimization. This second-order optimization scheme has been constructed to provide…

Chemical Physics · Physics 2021-09-15 Matthew S. Ryley , Michael Withnall , Tom J. P. Irons , Trygve Helgaker , Andrew M. Teale

Multi-configurational wave-function theory (MC-WFT) that combines complete active space self-consistent field (CASSCF) approach with subsequent state interaction (SI) treatment of spin-orbit coupling (SOC), abbreviated as CASSCF-SO, plays…

Chemical Physics · Physics 2025-03-11 Zhe-Bin Guan , Hong Jiang

This paper presents a novel Riemannian conjugate gradient method for the Kohn-Sham energy minimization problem in density functional theory (DFT), with a focus on non-metallic crystal systems. We introduce an energy-adaptive metric that…

Numerical Analysis · Mathematics 2025-03-21 Daniel Peterseim , Jonas Püschel , Tatjana Stykel