High-level coupled-cluster energetics by merging moment expansions with selected configuration interaction

Gururangan, Karthik; Deustua, J. Emiliano; Piecuch, Piotr

doi:10.1063/5.0064400

Cited by 18 publications

(13 citation statements)

References 118 publications

(196 reference statements)

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“…The initial CC(P ) calculations capture the leading higher-than-doubly excited components of the cluster operator T relevant to the problem of interest, while relaxing the low-order T n clusters, such as T 1 and T 2 , in the presence of their higher-order counterparts with n > 2, which is important for an accurate description of MR situations, especially bond breaking and biradicals, within a SRCC framework. [50][51][52][53][95][96][97][98]102 The noniterative corrections δ(P ; Q), which resemble biorthogonal moment expansions that were used in the past to formulate the left-eigenstate CR-CC approaches, such as CR-CC(2,3), [54][55][56][57][58] correct the CC(P ) energies for the remaining correlation effects that cannot be captured by performing the CC calculations in the P space. One can consider several different ways of setting up the P and Q spaces in the CC(P ;Q) calculations.…”

Section: Discussionmentioning

confidence: 99%

“…One can consider several different ways of setting up the P and Q spaces in the CC(P ;Q) calculations. [50][51][52][53]59,65,[95][96][97]102 In this work, we have focused on the semi-stochastic formulation of the CC(P ;Q) formalism, introduced in Ref. 95 and further developed in Refs.…”

Section: Discussionmentioning

confidence: 99%

“…We employed this geometry for two reasons. One of them is the fact that we used the same geometry in our earlier CIQMC-and CCMC-based, 95,97 CIPSI-driven, 102 and active-orbitalbased 51 CC(P ;Q) calculations for cyclobutadiene, when examining its automerization. Because of this, we could verify the correctness of our FCIQMC-driven CC(P ;Q) calculations for the lowest-energy singlet state, which is also the ground state of the system.…”

Section: Cyclobutadiene and Cyclopentadienyl Cationmentioning

confidence: 99%

“…98). Our group has also explored the deterministic alternative to the semi-stochastic CC(P ;Q) methodology by replacing the CIQMC and CCMC propagations, needed to identify the dominant higher-than-doubly excited components of T , by the sequences of Hamiltonian diagonalizations defining the selected CI approach abbreviated as CIPSI, [99][100][101] obtaining encouraging results, 102 but the main objective of this study is to continue examining the CIQMC-driven CC(P ;Q) methodology.…”

Section: Introductionmentioning

confidence: 99%

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Benchmarking the Semi-Stochastic CC(P;Q) Approach for Singlet-Triplet Gaps in Biradicals

Chakraborty,

Yuwono,

Deustua

et al. 2022

Preprint

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We recently developed a semi-stochastic approach to converging high-level coupled-cluster (CC) energetics, such as those obtained in the CC calculations with singles, doubles, and triples (CCSDT), in which the deterministic CC(P ;Q) framework is merged with the stochastic configuration interaction Quantum Monte Carlo (CIQMC) propagations [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017)]. In this work, we investigate the ability of the semi-stochastic CC(P ;Q) methodology to recover the CCSDT energies of the lowest singlet and triplet states and the corresponding singlet-triplet gaps of biradical systems using methylene, (HFH)− , cyclobutadiene, cyclopentadienyl cation, and trimethylenemethane as representative examples. We demonstrate that the semi-stochastic CC(P ;Q) calculations are capable of generating results of the CCSDT quality and improving the singlet-triplet gaps obtained with the triples corrections to CCSD defining the CR-CC(2,3) approach out of the early stages of CIQMC propagations.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Cyclobutadiene and Cyclopentadienyl Cationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Benchmarking the Semi-Stochastic CC(P;Q) Approach for Singlet-Triplet Gaps in Biradicals

Chakraborty,

Yuwono,

Deustua

et al. 2022

Preprint

Self Cite

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“…The methods of moments of coupled cluster equations (MMCC) and ensuing class of renormalized CC formalisms [87][88][89][92][93][94][122][123][124][125][126][127][128][129][130][131][132][133] have evolved into one of the most accurate methodologies for the high-precision evaluation of ground-state energies for chemical and nuclear systems. The idea of the MMCC approach is based on the asymmetric energy functional…”

Section: Many-body Formulation Of the Methods Of Moments Of Coupled C...mentioning

confidence: 99%

Mapping renormalized coupled cluster methods to quantum computers through a compact unitary representation of non-unitary operators

Peng¹,

Kowalski²

2022

Preprint

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Making quantum chemistry compressive and expressive: Toward practical ab‐initio simulation

Yang

2024

WIREs Comput Mol Sci

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Ab‐initio quantum chemistry simulations are essential for understanding electronic structure of molecules and materials in almost all areas of chemistry. A broad variety of electronic structure theories and implementations has been developed in the past decades to hopefully solve the many‐body Schrödinger equation in an approximate manner on modern computers. In this review, we present recent progress in advancing low‐rank electronic structure methodologies that rely on the wavefunction sparsity and compressibility to select the important subset of electronic configurations for both weakly and strongly correlated molecules. Representative chemistry applications that require the many‐body treatment beyond traditional density functional approximations are discussed. The low‐rank electronic structure theories have further prompted us to highlight compressive and expressive principles that are useful to catalyze idea of quantum learning models. The intersection of the low‐rank correlated feature design and the modern deep neural network learning provides new feasibilities to predict chemically accurate correlation energies of unknown molecules that are not represented in the training dataset. The results by others and us are discussed to reveal that the electronic feature sets from an extremely low‐rank correlation representation, which is very poor for explicit energy computation, are however sufficiently expressive for capturing and transferring electron correlation patterns across distinct molecular compositions, bond types and geometries.This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Software > Quantum Chemistry Software > Simulation Methods

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High-level coupled-cluster energetics by merging moment expansions with selected configuration interaction

Abstract: Inspired by our earlier semi-stochastic work aimed at converging high-level coupled-cluster (CC) energetics [

Cited by 18 publications

References 118 publications

Benchmarking the Semi-Stochastic CC(P;Q) Approach for Singlet-Triplet Gaps in Biradicals

Benchmarking the Semi-Stochastic CC(P;Q) Approach for Singlet-Triplet Gaps in Biradicals

Mapping renormalized coupled cluster methods to quantum computers through a compact unitary representation of non-unitary operators

Making quantum chemistry compressive and expressive: Toward practical ab‐initio simulation

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