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We demonstrate that, rather than resorting to high-cost dynamic correlation methods, qualitative failures in excited-state potential energy surface predictions can often be remedied at no additional cost by ensuring that optimal molecular…

Chemical Physics · Physics 2020-06-18 Lan Nguyen Tran , Eric Neuscamman

A systematic method for determining correlated wavefunctions of extended systems in the ground and excited states is presented. It allows to fully exploit the power of quantum-chemical programs designed for correlation calculations of…

Other Condensed Matter · Physics 2007-05-23 V. Bezugly

In order to explore the effects of high levels of electron correlation on the real-time coupled cluster formalism and algorithmic behavior, we introduce a time-dependent implementation of the CC3 singles, doubles and approximate triples…

Chemical Physics · Physics 2025-01-23 Zhe Wang , Håkon Emil Kristiansen , Thomas Bondo Pedersen , T. Daniel Crawford

In this paper, we develop a theoretical framework that extends single-reference (SR) coupled-cluster (CC) theory beyond its conventional role of describing a single electronic state-typically the lowest-energy state within the symmetry…

Quantum Physics · Physics 2026-02-17 Karol Kowalski , Nicholas P. Bauman

In this article, we present new results of high-order coupled cluster method (CCM) calculations, based on a N\'eel model state with spins aligned in the $z$-direction, for both the ground- and excited-state properties of the spin-half {\it…

Strongly Correlated Electrons · Physics 2013-05-30 R. F. Bishop , D. J. J. Farnell , S. E. Krueger , J. B. Parkinson , J. Richter , C. Zeng

We present a coupled cluster method (CCM) with optimized excitation operators. The efficiency comes from a parameterized form of excitation operators. The parameters are found by variational optimization procedure. The resultant number of…

Strongly Correlated Electrons · Physics 2014-12-09 Quanlin Jie

An efficient excited state method, named xCDFCI, in the configuration interaction framework, is proposed. xCDFCI extends the unconstrained nonconvex optimization problem in coordinate descent full configuration interaction~(CDFCI) to a…

Chemical Physics · Physics 2023-08-23 Zhe Wang , Zhiyuan Zhang , Jianfeng Lu , Yingzhou Li

We report ground- and excited-state dipole moments and oscillator strengths (computed in different ``gauges'' or representations) of full configuration interaction (FCI) quality using the selected configuration interaction method known as…

An extensive analysis has been carried out of the performance of standard families of basis sets with the hierarchy of coupled cluster methods CC2, CCSD, CC3 and CCSDT in computing selected Oxygen, Carbon and Nitrogen K-edge (vertical) core…

Chemical Physics · Physics 2019-08-13 Johanna P. Carbone , Lan Cheng , Rolf H. Myhre , Devin Matthews , Henrik Koch , Sonia Coriani

We extend our recently-developed heat-bath configuration interaction (HCI) algorithm, and our semistochastic algorithm for performing multireference perturbation theory, to the calculation of excited-state wavefunctions and energies. We…

Strongly Correlated Electrons · Physics 2017-11-22 Adam A. Holmes , C. J. Umrigar , Sandeep Sharma

We present a detailed derivation and discussion of cavity Born-Oppenheimer coupled cluster (CBO-CC) theory and address cavity-modified electron correlation in the vibrational strong coupling regime. Methodologically, we combine the recently…

Chemical Physics · Physics 2025-12-02 Eric W. Fischer

The phenomenon of orbital relaxation upon excitation of core electrons is a major problem in the linear-response treatment of core-hole spectroscopies. Rather than addressing relaxation through direct dynamical correlation of the excited…

Chemical Physics · Physics 2025-03-26 Megan Simons , Devin A. Matthews

Excited states in molecules can be difficult to investigate and generally require methods that are either computationally expensive or are not universally accurate. Recent research has focused on using higher-energy Slater determinants as…

Chemical Physics · Physics 2023-01-26 Diana-Gabriela Oprea , Hugh G. A. Burton

A relativistic version of the coupled-cluster single-double (CCSD) method is developed for atoms with a single valence electron. In earlier work, a linearized version of the CCSD method (with extensions to include a dominant class of triple…

Atomic Physics · Physics 2009-11-13 Rupsi Pal , M. S. Safronova , W. R. Johnson , Andrei Derevianko , Sergey G. Porsev

Inspired by our earlier semi-stochastic work aimed at converging high-level coupled-cluster (CC) energetics [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017); J. Chem. Phys. 154, 124103 (2021)], we propose a novel…

Chemical Physics · Physics 2022-10-06 Karthik Gururangan , J. Emiliano Deustua , Jun Shen , Piotr Piecuch

The equation of motion coupled cluster singles and doubles model (EOM-CCSD) is an accurate, black-box correlated electronic structure approach to investigate electronically excited states and electron attachment or detachment processes. It…

Chemical Physics · Physics 2023-09-18 Loïc Halbert , Andre Severo Pereira Gomes

We present a novel and cost-effective approach of using a second similarity transformation of the Hamiltonian to include the missing higher-order terms in the second-order approximate coupled cluster singles and doubles (CC2) model. The…

Chemical Physics · Physics 2022-01-26 Soumi Haldar , Achintya Kumar Dutta

We systematically investigate the calculation of excited states in quantum chemistry using auxiliary field quantum Monte Carlo (AFQMC). Symmetry allows targeting of the lowest triplet excited states in AFQMC based on restricted open-shell…

Chemical Physics · Physics 2025-09-16 Ankit Mahajan , Sandeep Sharma , Shiwei Zhang , David R. Reichman

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

We discuss diagrammatic modifications to the coupled cluster doubles (CCD) equations, wherein different groups of terms out of rings, ladders, crossed-rings and mosaics can be removed to form approximations to the coupled cluster method, of…

Chemical Physics · Physics 2014-05-06 James J. Shepherd , Thomas. M. Henderson , Gustavo E. Scuseria