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We report the analytical nuclear gradient theory for complete active space second-order perturbation theory (CASPT2) with imaginary shift, which is commonly used to avoid divergence of the perturbation expression. Our formulation is based…

Chemical Physics · Physics 2019-04-16 Jae Woo Park , Rachael Al-Saadon , Nils E. Strand , Toru Shiozaki

We present the formulation and implementation of an analytical gradient algorithm for extended multiconfiguration quasidegenerate perturbation theory (XMCQDPT2) with the resolvent-fitting approximation by Granovsky. This algorithm is…

Chemical Physics · Physics 2021-08-30 Jae Woo Park

The accurate resolution of the chemical properties of strongly correlated systems, such as biradicals, requires the use of electronic structure theories that account for both multi-reference as well as dynamic correlation effects. A variety…

Chemical Physics · Physics 2023-01-03 Jan-Niklas Boyn , David A. Mazziotti

Coupled-cluster theory with single and double excitations (CCSD) is a promising ab initio method for the electronic structure of three-dimensional metals, for which second-order perturbation theory (MP2) diverges in the thermodynamic limit.…

Materials Science · Physics 2021-06-16 James M. Callahan , Malte F. Lange , Timothy C. Berkelbach

UGA-SSMRPT2, the spin-free perturbative analogue of Mukerjee's State-Specific Multireference Coupled Cluster Theory (MkMRCC) is known to be successful for size-extensive and intruder-free construction of dissociation curves. This work…

Chemical Physics · Physics 2026-02-05 Shamik Chanda , Pratyush Bhattacharjya , Avijit Sen , Sangita Sen

We present second-order molecular cluster perturbation theory (MCPT(2)), a linear scaling methodology to calculate arbitrarily large systems with explicit calculation of individual wavefunctions in a coupled-cluster framework. This new…

Complete active space self-consistent field (CASSCF) computations can be realized at polynomial cost via the variational optimization of the active-space two-electron reduced-density matrix (2-RDM). Like conventional approaches to CASSCF,…

Chemical Physics · Physics 2018-12-10 Mohammad Mostafanejad , A. Eugene DePrince

In the previous paper of this series [JCTC 2020, 16, 3757], we presented a theoretical and algorithmic framework based on a localized representation of the occupied space that exploits the inherent sparsity in the real-space evaluation of…

Materials Science · Physics 2021-11-16 Hsin-Yu Ko , Biswajit Santra , Robert A. DiStasio

Based on 280 reference vertical transition energies of various natures (singlet, triplet, valence, Rydberg, $n\to\pi^*$, $\pi\to\pi^*$, and double excitations) extracted from the QUEST database, we assess the accuracy of third-order…

Chemical Physics · Physics 2022-07-04 Martial Boggio-Pasqua , Denis Jacquemin , Pierre-François Loos

We present a method for finding individual excited states' energy stationary points in complete active space self-consistent field theory that is compatible with standard optimization methods and highly effective at overcoming difficulties…

Strongly Correlated Electrons · Physics 2019-04-12 Lan Nguyen Tran , Jacqueline A. R. Shea , Eric Neuscamman

Intramolecular symmetry-adapted perturbation theory (ISAPT) is a method to compute and decompose the noncovalent interaction energy between two molecular fragments A and B connected via a linker C. The existing ISAPT algorithm displays…

Chemical Physics · Physics 2022-09-13 Du Luu , Konrad Patkowski

The original formulation (Phys. Rev. Lett. 119, 063002, 2017) of the natural orbital functional - second-order M{\o}ller-Plesset (NOF-MP2) method is based on the MP2 that uses the canonical Hartree-Fock molecular orbitals. The current work…

Chemical Physics · Physics 2018-08-22 Mario Piris

This chapter presents the theory behind the CASPT2 method and its adaptation to a multi-state formalism. The chapter starts with an introduction of the theory of the CASPT2 method - an application of Rayleigh-Schr\"odinger perturbation…

Chemical Physics · Physics 2023-05-12 Stefano Battaglia , Ignacio Fdez. Galván , Roland Lindh

We present a variational function that targets excited states directly based on their position in the energy spectrum, along with a Monte Carlo method for its evaluation and minimization whose cost scales polynomially for a wide class of…

Strongly Correlated Electrons · Physics 2016-01-22 Luning Zhao , Eric Neuscamman

We present an approach to renormalized second-order Green's function perturbation theory (GF2) which avoids all dependency on continuous variables, grids or explicit Green's functions, and is instead formulated entirely in terms of static…

Chemical Physics · Physics 2020-06-26 Oliver J. Backhouse , Max Nusspickel , George H. Booth

Guided by previous non-perturbative lattice simulations of a two-step electroweak phase transition, we reformulate the perturbative analysis of equilibrium thermodynamics for generic cosmological phase transitions in terms of effective…

High Energy Physics - Phenomenology · Physics 2023-09-06 Oliver Gould , Tuomas V. I. Tenkanen

Conventional full-waveform inversion (FWI) using the least-squares norm ($L^2$) as a misfit function is known to suffer from cycle skipping. This increases the risk of computing a local rather than the global minimum of the misfit. In our…

Geophysics · Physics 2017-05-12 Yunan Yang , Björn Engquist , Junzhe Sun , Brittany D. Froese

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

The Phase-Field Method (PFM) is employed to simulate two-phase flows with the fully-coupled Cahn-Hilliard-Navier-Stokes (CHNS) equations governing the temporal evolution. The methodology minimizes the total energy functional, accounting for…

Orbital-optimized density functional theory (DFT) has emerged as an alternative to time-dependent (TD) DFT capable of describing difficult excited states with significant electron density redistribution, such as charge-transfer, Rydberg,…

Chemical Physics · Physics 2025-01-22 Hanh D. M. Pham , Rustam Z. Khaliullin