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Size extensivity, defined as the correct scaling of energy with system size, is a desirable property for any many-body method. Traditional CI methods are not size extensive hence the error increases as the system gets larger. Coupled…

Chemical Physics · Physics 2022-07-27 Vibin Abraham , Nicholas J. Mayhall

The exponential computational cost of describing strongly correlated electrons can be mitigated by adopting a reduced density-matrix (RDM)-based description of the electronic structure. While variational two-electron RDM (v2RDM) methods can…

Chemical Physics · Physics 2026-01-06 Grier M. Jones , Run. R. Li , A. Eugene DePrince , Konstantinos D. Vogiatzis

For many-electron systems, the second-order reduced density matrix (2-RDM) provides sufficient information for characterizing their properties of interests in physics and chemistry, ranging from total energy, magnetism, quantum correlation…

Quantum Physics · Physics 2021-05-12 Yimin Li

Machine learning is rapidly accelerating materials and chemical discovery, but most current models target energies, forces, or selected molecular properties rather than the underlying many-body electronic structure. Learning…

The direct variational optimization of the two-electron reduced density matrix (2RDM) can provide a reference-independent description of the electronic structure of many-electron systems that naturally captures strong or nondynamic…

Chemical Physics · Physics 2024-06-19 Run R. Li , Marcus D. Liebenthal , A. Eugene DePrince

The two-electron reduced density matrix (2RDM) carries enough information to evaluate the electronic energy of a many-electron system. The variational 2RDM (v2RDM) approach seeks to determine the 2RDM directly, without knowledge of the wave…

Chemical Physics · Physics 2023-12-19 A. Eugene DePrince

Encoding the electronic structure of molecules using 2-electron reduced density matrices (2RDMs) as opposed to many-body wave functions has been a decades-long quest as the 2RDM contains sufficient information to compute the exact molecular…

Chemical Physics · Physics 2022-08-11 David Pekker , Chungwen Liang , Sankha Pattanayak , Swagatam Mukhopadhyay

An active space variational calculation of the 2-electron reduced density matrix (2-RDM) is derived and implemented where the active orbitals are correlated within the pair approximation. The pair approximation considers only doubly…

Chemical Physics · Physics 2020-10-13 Kade Head-Marsden , David A. Mazziotti

The second-order reduced density matrix method (the RDM method) has performed well in determining energies and properties of atomic and molecular systems, achieving coupled-cluster singles and doubles with perturbative triples (CC SD(T))…

Strongly Correlated Electrons · Physics 2012-07-23 James S. M. Anderson , Maho Nakata , Ryo Igarashi , Katsuki Fujisawa , Makoto Yamashita

We present an analytical proof and numerical demonstrations of the equivalence of the correlation energy from particle-particle random phase approximation (pp-RPA) and ladder-couple-cluster-doubles (ladder-CCD). These two theories reduce to…

Chemical Physics · Physics 2013-11-01 Degao Peng , Stephan N. Steinmann , Helen van Aggelen , Weitao Yang

A combined density and first-order reduced-density-matrix (1RDM) functional method is proposed for the calculation of potential energy curves (PECs) of molecular multibond dissociation. Its 1RDM functional part, a pair density functional,…

Chemical Physics · Physics 2020-09-23 Robert van Meer , Oleg Gritsenko , Jeng-Da Chai

Correlation-driven phenomena in molecular periodic systems are challenging to predict computationally not only because such systems are periodically infinite but also because they are typically strongly correlated. Here we generalize the…

Chemical Physics · Physics 2022-04-18 Simon Ewing , David A. Mazziotti

We recently presented a constructive solution to the N-representability problem of the two-electron reduced density matrix (2-RDM)---a systematic approach to constructing complete conditions to ensure that the 2-RDM represents a realistic…

Chemical Physics · Physics 2012-07-04 David A. Mazziotti

In methods like geminal-based approaches or coupled cluster that are solved using the projected Schr\"odinger equation, direct computation of the 2-electron reduced density matrix (2-RDM) is impractical and one falls back to a 2-RDM based…

Minimizing the energy of an $N$-electron system as a functional of a two-electron reduced density matrix (2-RDM), constrained by necessary $N$-representability conditions (conditions for the 2-RDM to represent an ensemble $N$-electron…

Chemical Physics · Physics 2016-06-21 Nicholas C. Rubin , David A. Mazziotti

We present a constructive solution to the N-representability problem---a full characterization of the conditions for constraining the two-electron reduced density matrix (2-RDM) to represent an N-electron density matrix. Previously known…

Quantum Physics · Physics 2012-07-04 David A. Mazziotti

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

Double excitations are crucial to understanding numerous chemical, physical, and biological processes, but accurately predicting them remains a challenge. In this work, we explore the particle-particle random phase approximation (ppRPA) as…

Chemical Physics · Physics 2024-11-26 Jincheng Yu , Jiachen Li , Tianyu Zhu , Weitao Yang

Two-body reduced density matrices (2RDMs) encode the essential two-electron physics of electronic states, but their quartic storage cost poses a major limitation in practical workflows. We investigate a simple protocol to compress both…

Chemical Physics · Physics 2026-05-15 Kemal Atalar , Hugh G. A. Burton , Andreas Grüneis , George H. Booth

We present the expansion to the expectation value coupled cluster theory (XCC) to the wavefunctions that include the inter electronic distances $r_{12}$ explicitly. We have extended our algebraic manipulation code \paldus to deal with the…

Chemical Physics · Physics 2023-04-25 Aleksandra M. Tucholska , Marcin Modrzejewski , Robert Moszynski
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