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We introduce a new variant of the complete active space second-order perturbation theory (CASPT2) method that performs similarly to multistate CASPT2 (MS-CASPT2) in regions of the potential energy surface where the electronic states are…

Chemical Physics · Physics 2022-04-12 Stefano Battaglia , Roland Lindh

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

We present analytic gradients and derivative couplings for the simplest possible multireference configuration interaction method, CIS-1D, an electronic structure ansatz that includes all single excitations and one lone double excitation on…

Chemical Physics · Physics 2021-02-15 Hung-Hsuan Teh , Joseph E. Subotnik

We report the development of the theory and computer program for analytical nuclear energy gradients for (extended) multi-state complete active space perturbation theory (CASPT2) with full internal contraction. The vertical shifts are also…

Chemical Physics · Physics 2017-03-20 Bess Vlaisavljevich , Toru Shiozaki

We propose a method for the evaluation of magnetic exchange couplings based on noncollinear spin-density functional calculations. The method employs the second derivative of the total Kohn-Sham energy of a single reference state, in…

Materials Science · Physics 2009-11-13 Juan E. Peralta , Veronica Barone

We propose the multi-state complete-active-space second-order perturbation theory spin-orbit method (MS-CASPT2-SO) for electronic structure calculations. It is a two-step spin-orbit coupling method that does not make use of energy shifts…

Chemical Physics · Physics 2010-12-30 Zoila Barandiaran , Luis Seijo

A partial-active-space (PAS) multi-state (MS) multi-reference second-order perturbation theory (MRPT2) for the electronic structure of strongly correlated systems of electrons, dubbed PASPT2, is formulated by linearizing the intermediate…

Chemical Physics · Physics 2026-05-21 Chunzhang Liu , Ning Zhang , Wenjian Liu

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 consider the application of Kramers theory to the microscopic calculation of rates of conformational transitions of macromolecules. The main difficulty in such an approach is to locate the transition state in a huge configuration space.…

Biomolecules · Quantitative Biology 2008-09-02 Marcello Sega , Pietro Faccioli , Francesco Pederiva , Henri Orland

A central pursuit in theoretical chemistry is the accurate simulation of photochemical reactions, which are governed by nonadiabatic transitions through conical intersections. Machine learning has emerged as a transformative tool for…

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

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

For years, theoretical calculations and scalable computer simulations have complemented ultrafast experiments as they offer the advantage to overcome experimental restrictions and have access to the whole dynamics. This synergy between…

Chemical Physics · Physics 2024-02-20 Patricia Vindel-Zandbergen , Jesús González-Vázquez

The $\Delta \text{NO}$ method for static correlation is combined with second-order M{\o}ller-Plesset perturbation theory (MP2) and coupled-cluster singles and doubles (CCSD) to account for dynamic correlation. The MP2 and CCSD expressions…

Chemical Physics · Physics 2020-06-05 Joshua W. Hollett , Pierre-François Loos

We present an accurate method for calculating hyperfine coupling constants (HFCCs) based on the complete active space second-order perturbation theory (CASPT2) with full internal contraction. The HFCCs are computed as a first-order property…

Chemical Physics · Physics 2017-03-20 Toru Shiozaki , Takeshi Yanai

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

A hybrid stochastic-deterministic approach for computing the second-order perturbative contribution $E^{(2)}$ within multireference perturbation theory (MRPT) is presented. The idea at the heart of our hybrid scheme --- based on a…

Chemical Physics · Physics 2018-05-31 Yann Garniron , Anthony Scemama , Pierre-François Loos , Michel Caffarel

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

Calculating excited-state gradients and derivative couplings using time-dependent density functional theory (TDDFT) remains a computationally demanding task. An efficient variant, TDDFT with resolution of the identity and a minimal…

Chemical Physics · Physics 2025-11-26 Zhichen Pu , Xiaojie Wu , Yuanheng Wang , Cheng Fan , Wen Yan , Zehao Zhou , Yi Qin Gao , Qiming Sun

Ab initio methods based on the second-order and higher connected moments, or cumulants, of a reference function have seen limited use in the determination of correlation energies of chemical systems throughout the years. Moment-based…

Chemical Physics · Physics 2023-08-25 Brad Ganoe , Martin Head-Gordon
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