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We introduce QRDM-NEVPT2: a hybrid quantum-classical implementation of strongly-contracted N-electron Valence State $2^{nd}$-order Perturbation Theory (SC-NEVPT2), in which the Complete Active Space Configuration Interaction (CASCI) step,…

Quantum Physics · Physics 2022-10-13 Michal Krompiec , David Muñoz Ramo

In earlier work [J. Chem. Phys. 144, 064102 (2016)], we introduced a time-dependent formulation of the second-order N-electron valence perturbation theory (t-NEVPT2) which (i) had a lower computational scaling than the usual…

Chemical Physics · Physics 2018-04-09 Alexander Sokolov , Sheng Guo , Enrico Ronca , Garnet Kin-Lic Chan

An analytical gradient theory for single-state N-electron valence state perturbation theory (NEVPT2), using both strongly contracted (SC) and partially contracted (PC) internal contraction schemes, is developed. We demonstrate the utility…

Chemical Physics · Physics 2020-12-16 Jae Woo Park

We present a measurement-cost efficient implementation of Strongly-Contracted $N$-Electron Valence Perturbation Theory (SC-NEVPT2) for use on near-term quantum devices. At the heart of our algorithm we exploit the properties of adaptive…

Quantum Physics · Physics 2024-05-27 Aaron Fitzpatrick , N. Walter Talarico , Roberto Di Remigio Eikås , Stefan Knecht

We present a second-order N-electron valence state perturbation theory (NEVPT2) based on a density matrix renormalization group (DMRG) reference wave function that exploits a Cholesky decomposition of the two-electron repulsion integrals…

Chemical Physics · Physics 2017-03-07 Leon Freitag , Stefan Knecht , Celestino Angeli , Markus Reiher

We report internally contracted relativistic multireference configuration interaction (ic-MRCI), complete active space second-order perturbation (CASPT2), and strongly contracted n-electron valence state perturbation theory (NEVPT2) on the…

Chemical Physics · Physics 2015-12-31 Toru Shiozaki , Wataru Mizukami

We present two efficient and intruder-free methods for treating dynamic correlation on top of general multi-configuration reference wave functions---including such as obtained by the density matrix renormalization group (DMRG) with large…

Chemical Physics · Physics 2016-09-13 Sandeep Sharma , Gerald Knizia , Sheng Guo , Ali Alavi

We identify the dominant computational cost within the recently introduced stochastic and internally contracted FCIQMC-NEVPT2 method for large active space sizes. This arises from the contribution to the four-body intermediates arising from…

Chemical Physics · Physics 2020-10-05 James J. Halson , Robert J. Anderson , George H. Booth

In the present article, we show how to formulate the partially contracted n-electron valence second order perturbation theory (NEVPT2) energies in the atomic and active molecular orbital basis by employing the Laplace transformation of…

Chemical Physics · Physics 2017-06-28 Benjamin Helmich-Paris , Stefan Knecht

We introduce an algorithm that can be used to perform stochastic perturbation theory (sPT) to correct any non-linearly parametrized wavefunction that can be optimized using orbital space Variational Monte Carlo (VMC). Although the…

Strongly Correlated Electrons · Physics 2018-03-13 Sandeep Sharma

Full Configuration Interaction Quantum Monte Carlo (FCIQMC) has been effectively applied to very large configuration interaction (CI) problems, and was recently adapted for use as an active space solver and combined with orbital…

Chemical Physics · Physics 2020-02-19 Robert J. Anderson , Toru Shiozaki , George H. Booth

Multi-configurational wave-function theory (MC-WFT) that combines complete active space self-consistent field (CASSCF) approach with subsequent state interaction (SI) treatment of spin-orbit coupling (SOC), abbreviated as CASSCF-SO, plays…

Chemical Physics · Physics 2025-03-11 Zhe-Bin Guan , Hong Jiang

Given a number of datasets for evaluating the performance of single reference methods for the low-lying excited states of closed-shell molecules, a comprehensive dataset for assessing the performance of multireference methods for the…

Chemical Physics · Physics 2024-11-07 Yangyang Song , Ning Zhang , Yibo Lei , Yang Guo , Wenjian Liu

Methods able to simultaneously account for both static and dynamic electron correlations have often been employed, not only to model photochemical events, but also to provide reference values for vertical transition energies, hence allowing…

Chemical Physics · Physics 2022-04-26 Rudraditya Sarkar , Pierre-François Loos , Martial Boggio-Pasqua , Denis Jacquemin

Ab initio description of point defects in semiconductors, characterized by in-gap states of significant multideterminant character, presents a longstanding theoretical challenge for density functional theory (DFT) methods. In this study, we…

Materials Science · Physics 2024-11-27 Zsolt Benedek , Ádám Ganyecz , Anton Pershin , Viktor Ivády , Gergely Barcza

Analytic energy gradients are presented for a variational two-electron reduced-density-matrix-driven complete active space self-consistent field (v2RDM-CASSCF) procedure that employs the density-fitting (DF) approximation to the…

Chemical Physics · Physics 2018-11-29 J. Wayne Mullinax , Evgeny Epifanovsky , Gergely Gidofalvi , A. Eugene DePrince

We present the first implementation of spin-orbit coupling effects in fully internally contracted second-order quasidegenerate N-electron valence perturbation theory (SO-QDNEVPT2). The SO-QDNEVPT2 approach enables the computations of…

Chemical Physics · Physics 2023-03-07 Rajat Majumder , Alexander Yu. Sokolov

A degenerate perturbation $k\cdot p$ approach for effective mass calculations is implemented in the all-electron density functional theory (DFT) package WIEN2k. The accuracy is tested on major group IVA, IIIA-VA, and IIB-VIA semiconductor…

Materials Science · Physics 2022-01-06 Oleg Rubel , Fabien Tran , Xavier Rocquefelte , Peter Blaha

Multireference density functional theory (MR-DFT) has been a pivotal method for studying nuclear low-lying states and neutrinoless double-beta ($0\nu\beta\beta$) decay. However, quantifying their theoretical uncertainties has been a…

Nuclear Theory · Physics 2025-08-26 X. Zhang , C. C. Wang , C. R. Ding , J. M. Yao

The computationally expensive evaluation and storage of high-rank reduced density matrices (RDMs) has been the bottleneck in the calculation of dynamic correlation for multireference wave functions in large active spaces. We present a…

Chemical Physics · Physics 2020-01-08 Ankit Mahajan , Nick S. Blunt , Iliya Sabzevari , Sandeep Sharma
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