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The semistochastic heat-bath configuration interaction (SHCI) method is a selected configuration interaction plus perturbation theory method that has provided near-full configuration interaction (FCI) levels of accuracy for many systems…

Chemical Physics · Physics 2021-11-30 Yuan Yao , Emmanuel Giner , Tyler A. Anderson , Julien Toulouse , C. J. Umrigar

Finding the ground state of a fermionic Hamiltonian using quantum Monte Carlo is a very difficult problem, due to the Fermi sign problem. While still scaling exponentially, full configuration-interaction Monte Carlo (FCI-QMC) mitigates some…

Computational Physics · Physics 2013-12-17 Michael H. Kolodrubetz , Bryan K. Clark

In a previous work (arXiv:2010.02027) we showed how the full configuration interaction (FCI) ground state energy can be obtained as a functional of an arbitrary reference wavefunction by means of a gradient descent or quasi-Newton…

Chemical Physics · Physics 2020-12-10 Carlos A. Jiménez-Hoyos

The inherently high computational cost of iterative self-consistent-field (SCF) methods proves to be a critical issue delaying visual and haptic feedback in real-time quantum chemistry. In this work, we introduce two schemes for SCF…

Chemical Physics · Physics 2016-03-10 Adrian H. Mühlbach , Alain C. Vaucher , Markus Reiher

Quantum Selected Configuration Interaction (QSCI) methods (also known as Sample-based Quantum Diagonalization, SQD) have emerged as promising near-term approaches to solving the electronic Schr{\"o}dinger equation with quantum computers. In…

We extend the scope of full configuration interaction quantum Monte Carlo (FCIQMC) to be applied to coupled fermion-boson hamiltonians, alleviating the a priori truncation in boson occupation which is necessary for many other wave function…

Strongly Correlated Electrons · Physics 2022-11-09 Robert J. Anderson , Charles C. J. Scott , George H. Booth

We consider gradient descent and quasi-Newton algorithms to optimize the full configuration interaction (FCI) ground state wavefunction starting from an arbitrary reference state $|0 \rangle$. We show that the energies obtained along the…

Chemical Physics · Physics 2021-02-03 Carlos A. Jiménez-Hoyos

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

In a recent paper, we proposed the adaptive shift method for correcting the undersampling bias of the initiator-FCIQMC. The method allows faster convergence with the number of walkers to the FCI limit than the normal initiator method,…

Computational Physics · Physics 2021-02-03 Khaldoon Ghanem , Kai Guther , Ali Alavi

The combinatorial scaling of configuration interaction (CI) has long restricted its applicability to only the simplest molecular systems. Here, we report the first numerically exact CI calculation exceeding one quadrillion ($10^{15}$)…

Chemical Physics · Physics 2025-12-16 Agam Shayit , Can Liao , Shiv Upadhyay , Hang Hu , Tianyuan Zhang , Eugene DePrince , Chao Yang , Xiaosong Li

Approximate full configuration interaction (FCI) calculations have recently become tractable for systems of unforeseen size thanks to stochastic and adaptive approximations to the exponentially scaling FCI problem. The result of an FCI…

Strongly Correlated Electrons · Physics 2017-10-25 Susi Lehtola , Norm M. Tubman , K. Birgitta Whaley , Martin Head-Gordon

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

Development of exponentially scaling methods has seen great progress in tackling larger systems than previously thought possible. One such technique, full configuration interaction quantum Monte Carlo, is a useful algorithm that allows…

Strongly Correlated Electrons · Physics 2016-08-23 Norm M. Tubman , Joonho Lee , Tyler Y. Takeshita , Martin Head-Gordon , K. Birgitta Whaley

Stable partitioned techniques for simulating unsteady fluid-structure interaction (FSI) are known to be computationally expensive when high added-mass is involved. Multiple coupling strategies have been developed to accelerate these…

Computational Engineering, Finance, and Science · Computer Science 2025-02-18 Azzeddine Tiba , Thibault Dairay , Florian de Vuyst , Iraj Mortazavi , Juan-Pedro Berro Ramirez

Facilitated by a rigorous partitioning of a molecular system's orbital basis into two fundamental subspaces - a reference and an expansion space, both with orbitals of unspecified occupancy - we generalize our recently introduced many-body…

Chemical Physics · Physics 2019-12-12 Janus J. Eriksen , Jürgen Gauss

We propose using the wave function generated by the quantum selected configuration interaction (QSCI) method as the trial wave function in phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC). In the QSCI framework, electronic…

A new approach is presented to improve the performance of semiempirical quantum mechanical (SQM) methods in the description of noncovalent interactions. To show the strategy, the PM6 Hamiltonian was selected, although, in general, the…

Modern quantum Monte Carlo (QMC) methods often capture electron correlation through both explicitly correlating Jastrow factors and small to mid-sized configuration interaction (CI) expansions. Here, we study the additional optimization…

Chemical Physics · Physics 2023-02-08 Scott M. Garner , Eric Neuscamman

Within Full Configuration Interaction Quantum Monte Carlo, we investigate how the statistical error behaves as a function of the parameters which control the stochastic sampling. We define the inefficiency as a measure of the statistical…

Chemical Physics · Physics 2016-03-15 W. A. Vigor , J. S. Spencer , M. J. Bearpark , A. J. W. Thom

We introduce an algorithm for sampling many-body quantum states in Fock space. The algorithm efficiently samples states with probability approximately proportional to an arbitrary function of the second-quantized Hamiltonian matrix element…

Strongly Correlated Electrons · Physics 2016-04-28 Adam Holmes , Hitesh J. Changlani , C. J. Umrigar