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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

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

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

We present a stochastic approach to perform strongly contracted n-electron valence state perturbation theory (SC-NEVPT), which only requires one- and two-body reduced density matrices, without introducing approximations. We use this method…

Chemical Physics · Physics 2021-01-05 Nick S. Blunt , Ankit Mahajan , Sandeep Sharma

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 a formulation and implementation of second-order quasidegenerate N-electron valence perturbation theory (QDNEVPT2) that provides a balanced and accurate description of spin-orbit coupling and dynamic correlation effects in…

Chemical Physics · Physics 2024-06-19 Rajat Majumder , Alexander Yu. Sokolov

We discuss the time-dependent formulation of perturbation theory in the context of the interacting zeroth-order Hamiltonians that appear in multi-reference situations. As an example, we present a time-dependent formulation and…

Chemical Physics · Physics 2018-04-09 Alexander Yu. Sokolov , Garnet K. -L. Chan

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

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 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

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

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

Excited-state methods within the nuclear--electronic orbital (NEO) framework have the potential to capture vibrational, electronic, and vibronic transitions in a single calculation. In the NEO approach, specified nuclei, typically protons,…

Chemical Physics · Physics 2026-03-16 Jonathan H. Fetherolf , Fabijan Pavošević , Sharon Hammes-Schiffer

The accurate description of nuclear quantum effects, such as zero-point energy, is important for modeling a wide range of chemical and biological processes. Within the nuclear-electronic orbital (NEO) approach, such effects are incorporated…

Chemical Physics · Physics 2022-09-07 Fabijan Pavošević , Sharon Hammes-Schiffer

The strong-coupling perturbation theory (SCPT) for correlated electron systems is extended to the case of full Coulomb interaction. The Coulomb mechanism of the orbital polarization is discussed and attention is paid to the importance of…

Strongly Correlated Electrons · Physics 2007-05-23 I. Sandalov , U. Lundin , O. Eriksson

Variational algorithms are a promising paradigm for utilizing near-term quantum devices for modeling electronic states of molecular systems. However, previous bounds on the measurement time required have suggested that the application of…

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

The electron pair approximation offers a resource efficient variational quantum eigensolver (VQE) approach for quantum chemistry simulations on quantum computers. With the number of entangling gates scaling quadratically with system size…

Accurately describing strong electron correlation in complex systems remains a prominent challenge in computational chemistry as near-term quantum algorithms treating total correlation often require prohibitively deep circuits. Here we…

Computational Engineering, Finance, and Science · Computer Science 2026-04-21 Zhanou Liu , Yuhao Chen , Yingjin Ma , Xiao He , Yuxin Deng

Nuclear quantum phenomena beyond the Born-Oppenheimer approximation are known to play an important role in a growing number of chemical and biological processes. While there exists no unique consensus on a rigorous and efficient…

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