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We present developments in the calculation of reduced density matrices (RDMs) in the full configuration interaction quantum Monte Carlo (FCIQMC) method. An efficient scheme is described to allow storage of RDMs across distributed memory,…

Computational Physics · Physics 2017-07-27 N. S. Blunt , George H. Booth , Ali Alavi

The accurate description of the non-linear response of many-electron systems to strong-laser fields remains a major challenge. Methods that bypass the unfavorable exponential scaling with particle number are required to address larger…

The reduced density matrix (RDM) plays a key role in quantum entanglement and measurement, as it allows the extraction of almost all physical quantities related to the reduced degrees of freedom. However, restricted by the degrees of…

Quantum Physics · Physics 2025-03-27 Bin-Bin Mao , Yi-Ming Ding , Zhe Wang , Shijie Hu , Zheng Yan

A direct orbital optimization method is presented for density functional calculations of excited electronic states using either a real space grid or a plane wave basis set. The method is variational, provides atomic forces in the excited…

Computational Physics · Physics 2022-11-09 Aleksei V. Ivanov , Gianluca Levi , Elvar Ö. Jónsson , Hannes Jónsson

We present a second-order formulation of multi-reference algebraic diagrammatic construction theory [Sokolov, A. Yu. J. Chem. Phys. 2018, 149, 204113] for simulating photoelectron spectra of strongly correlated systems (MR-ADC(2)). The…

Chemical Physics · Physics 2020-07-28 Koushik Chatterjee , Alexander Yu. Sokolov

Reduced density matrix functional theory (RDMFT) calculations are usually implemented in a decoupled manner, where the orbital and occupation optimizations are repeated alternately. Typically, orbital updates are performed using the unitary…

Chemical Physics · Physics 2024-09-04 Yi-Fan Yao , Neil Qiang Su

Reduced density-matrix functional theory (RDMFT) provides a variational route to electronic correlations beyond conventional density-functional approximations, but explicit evaluations of density-matrix functionals still scale exponentially…

Chemical Physics · Physics 2026-05-19 Konstantin Tamoev , Robert Schade , Thomas D. Kühne

We present fully empirical exchange-correlation functionals to be used within reduced density matrix functional theory (RDMFT). These are of the popular J-K form, where the function of the occupation numbers that multiplies the Fock orbital…

Computational Physics · Physics 2017-03-03 Miguel A. L. Marques , N. N. Lathiotakis

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

Unitary Coupled Cluster (UCC) theory is a promising variational method for electronic structure calculations, especially for strongly correlated systems and quantum computers. However, its practical application is limited by the steep…

Chemical Physics · Physics 2026-02-05 Prateek Vaish , Brenda Rubenstein

State-of-the-art many-body wave function techniques rely on heuristics to achieve high accuracy at an attainable cost to solve the many-body Schr\"odinger equation. By far the most common property used to assess accuracy has been the total…

Chemical Physics · Physics 2022-11-30 Shunyue Yuan , Yueqing Chang , Lucas K. Wagner

The computational demand posed by applying multi-Slater determinant trials in phaseless auxiliary-field quantum Monte Carlo methods (MSD-AFQMC) is particularly significant for molecules exhibiting strong correlations. Here, we propose using…

Chemical Physics · Physics 2023-12-27 Hung Q. Pham , Runsheng Ouyang , Dingshun Lv

A two-parameter extension of the density-scaled double hybrid approach of Sharkas et al. [J. Chem. Phys. 134, 064113 (2011)] is presented. It is based on the explicit treatment of a fraction of multideterminantal exact exchange. The…

Chemical Physics · Physics 2012-01-12 Emmanuel Fromager

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

We present \textsc{dm-PhiSNet}, a physically constrained \textsc{PhiSNet}-based equivariant model that predicts one-electron reduced density matrices (1-RDMs) directly from molecular geometries in an atomic-orbital (AO) basis for…

Chemical Physics · Physics 2026-05-01 Zuriel Y. Yescas-Ramos , Andrés Álvarez-García , Huziel E. Sauceda

The variational determination of the two-fermion reduced density matrix is described for harmonically trapped, ultracold few-fermion systems in one dimension with equal spin populations. This is accomplished by formulating the problem as a…

Quantum Gases · Physics 2022-11-11 Mitchell J. Knight , Harry M. Quiney , Andy M. Martin

Density functional theory (DFT), the most widely adopted method in modern computational chemistry, fails to describe accurately the electronic structure of strongly correlated systems. Here we show that DFT can be formally and practically…

Chemical Physics · Physics 2022-04-18 Daniel Gibney , Jan-Niklas Boyn , David A. Mazziotti

The density matrix renormalization group (DMRG) method allows for very precise calculations of ground state properties in low-dimensional strongly correlated systems. We investigate two methods to expand the DMRG to calculations of…

Condensed Matter · Physics 2009-10-31 Till D. Kuehner , Steven R. White

A variational formulation for the calculation of interacting fermion systems based on the density-matrix functional theory is presented. Our formalism provides for a natural integration of explicit many-particle effects into standard…

Strongly Correlated Electrons · Physics 2013-05-29 Peter E. Bloechl , Christian F. J. Walther , Thomas Pruschke

It is well-known that not only the orbital ordering but also the choice of the orbitals themselves as the basis may significantly influence the computational efficiency of density-matrix renormalization group (DMRG) calculations. In this…

Strongly Correlated Electrons · Physics 2013-06-14 Yingjin Ma , Haibo Ma