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Efficient analysis and simulation of multiscale stochastic systems of chemical kinetics is an ongoing area for research, and is the source of many theoretical and computational challenges. In this paper, we present a significant improvement…

Numerical Analysis · Mathematics 2016-09-21 Simon Cotter

Stochastic methods offer an effective way to suppress coherent errors in quantum simulation. In particular, the randomized compilation protocol may reduce circuit depth by randomly sampling Hamiltonian terms rather than following the…

Quantum Physics · Physics 2026-05-15 Yu-Xia Wu , Yun-Zhuo Fan , Dan-Bo Zhang

Unbiased stochastic sampling of the one- and two-body reduced density matrices is achieved in full configuration interaction quantum Monte Carlo with the introduction of a second, "replica" ensemble of walkers, whose population evolves in…

Computational Physics · Physics 2015-09-02 Robert E. Thomas , Daniel Opalka , Catherine Overy , Peter J. Knowles , Ali Alavi , George H. Booth

We present a new method for the optimization of large configuration interaction (CI) expansions in the quantum Monte Carlo (QMC) framework. The central idea here is to replace the non-orthogonal variational optimization of CI coefficients…

Chemical Physics · Physics 2022-05-26 Abdallah Ammar , Emmanuel Giner , Anthony Scemama

Full configuration interaction (FCI) solvers are limited to small basis sets due to their expensive computational costs. An optimal orbital selection for FCI (OptOrbFCI) is proposed to boost the power of existing FCI solvers to pursue the…

Chemical Physics · Physics 2020-09-01 Yingzhou Li , Jianfeng Lu

By performing a stochastic dynamic in a space of Slater determinants, the Full Configuration Interaction Quantum Monte Carlo (FCIQMC) method has been able to obtain energies which are essentially free from systematic error to the basis set…

Computational Physics · Physics 2014-10-10 George H. Booth , Deidre Cleland , Ali Alavi , David P. Tew

The formalism of the continuum random-phase approximation theory which treats, without ap- proximations, the continuum part of the single-particle spectrum, is extended to describe charge- exchange excitations. Our approach is…

Nuclear Theory · Physics 2016-04-05 V. De Donno , G. Co' , M. Anguiano , A. M. Lallena

In the present work, we present a hybrid quantum-classical workflow aimed at improving the accuracy of alchemical free energy (AFE) predictions by incorporating configuration interaction (CI) simulations using the book-ending correction…

Chemical Physics · Physics 2025-06-27 Milana Bazayeva , Zhen Li , Danil Kaliakin , Fangchun Liang , Akhil Shajan , Susanta Das , Kenneth M. Merz

This work develops and illustrates a new method of calculating "chemically accurate" electronic wavefunctions (and energies) via a truncated full configuration interaction (CI) procedure which arguably circumvents the large matrix…

Chemical Physics · Physics 2022-12-21 Stephen J. Cotton

Many-body simulations of quantum systems is an active field of research that involves many different methods targeting various computing platforms. Many methods commonly employed, particularly coupled cluster methods, have been adapted to…

Chemical Physics · Physics 2023-06-14 David B. Williams-Young , Norm M. Tubman , Carlos Mejuto-Zaera , Wibe A. de Jong

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

Due to the complexity of order statistics, the finite sample behaviour of robust statistics is generally not analytically solvable. While the Monte Carlo method can provide approximate solutions, its convergence rate is typically very slow,…

Methodology · Statistics 2024-09-12 Li Tuobang

We present a quantum algorithm for the simulation of molecular systems that is asymptotically more efficient than all previous algorithms in the literature in terms of the main problem parameters. As in previous work [Babbush et al., New…

We study several approaches to orbital optimization in selected configuration interaction plus perturbation theory (SCI+PT) methods, and test them on the ground and excited states of three molecules using the semistochastic heatbath…

Chemical Physics · Physics 2021-07-14 Yuan Yao , C. J. Umrigar

For optimal accuracy, auxiliary-field quantum Monte Carlo (AFQMC) requires trial states consisting of multiple Slater determinants. We develop an efficient algorithm to select the determinants from an AFQMC random walk eliminating the need…

Chemical Physics · Physics 2025-07-08 Zoran Sukurma , Martin Schlipf , Georg Kresse

We present a perturbative correction within initiator full configuration interaction quantum Monte Carlo (i-FCIQMC). In the existing i-FCIQMC algorithm, a significant number of spawned walkers are discarded due to the initiator criteria.…

Chemical Physics · Physics 2018-06-13 Nick S. Blunt

Fast Incremental Expectation Maximization (FIEM) is a version of the EM framework for large datasets. In this paper, we first recast FIEM and other incremental EM type algorithms in the {\em Stochastic Approximation within EM} framework.…

Machine Learning · Computer Science 2021-01-01 Gersende Fort , P. Gach , E. Moulines

Conformal prediction aims to determine precise levels of confidence in predictions for new objects using past experience. However, the commonly used exchangeable assumptions between the training data and testing data limit its usage in…

Machine Learning · Statistics 2022-10-18 Youhui Ye , Meimei Liu , Xin Xing

Sparse variational approximations are popular methods for scaling up inference and learning in Gaussian processes to larger datasets. For $N$ training points, exact inference has $O(N^3)$ cost; with $M \ll N$ features, state of the art…

Machine Learning · Statistics 2024-04-15 Talay M Cheema , Carl Edward Rasmussen

We present a novel implementation of the complete active space self-consistent field (CASSCF) method that makes use of the many-body expanded full configuration interaction (MBE-FCI) method to incrementally approximate electronic structures…