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Adapting a veritable many-body method to a system of non-interacting particles (NIP), while being trivial from a physical point of view, can be of interest with regard to methodological aspects. In this article we study the NIP versions of…

化学物理 · 物理学 2023-11-07 Jochen Schirmer

In single-reference coupled-cluster (CC) methods, one has to solve a set of non-linear polynomial equations in order to determine the so-called amplitudes which are then used to compute the energy and other properties. Although it is of…

化学物理 · 物理学 2021-09-10 Antoine Marie , Fábris Kossoski , Pierre-François Loos

The pair coupled cluster doubles (pCCD) method (where the excitation manifold is restricted to electron pairs) has a series of interesting features. Among others, it provides ground-state energies very close to what is obtained with…

We reexamine $\Delta$CCSD, a state-specific coupled-cluster (CC) with single and double excitations (CCSD) approach that targets excited states through the utilization of non-Aufbau determinants. This methodology is particularly efficient…

In this work, we derive working equations for the Linear Response pair Coupled Cluster Doubles (LR-pCCD) ansatz and its extension to singles (S), LR-pCCD+S. These methods allow us to compute electronic excitation energies and transition…

化学物理 · 物理学 2025-03-18 Somayeh Ahmadkhani , Katharina Boguslawsk , Paweł Tecmer

The accurate description of doubly-excited states using conventional electronic structure methods is remarkably challenging, primarily because such excited states require the inclusion of doubly or higher excited configurations or the…

化学物理 · 物理学 2019-05-01 Katharina Boguslawski

Accurate yet efficient modeling of chemical systems with pronounced static correlation in their excited states remains a significant challenge in quantum chemistry, as most electronic structure methods that can adequately capture static…

化学物理 · 物理学 2025-03-07 Sylvia J. Bintrim , Kevin Carter-Fenk

In the realm of photochemistry, the significance of double excitations (also known as doubly-excited states), where two electrons are concurrently elevated to higher energy levels, lies in their involvement in key electronic transitions…

Excited states exhibiting double excitation character are notoriously difficult to model using conventional single-reference methods, such as adiabatic time-dependent density-functional theory (TD-DFT) or equation-of-motion coupled cluster…

We introduce a new method for the computation of the transition moments between the excited electronic states based on the expectation value formalism of the coupled cluster theory [B. Jeziorski and R. Moszynski, Int. J. Quant. Chem. 48,…

化学物理 · 物理学 2017-02-01 Aleksandra Tucholska , Michal Lesiuk , Robert Moszynski

A unitary coupled-cluster (UCC)-based self-consistent electron propagator theory (EPT) is proposed for the description of electron-detached and electron-attached states. Two practical schemes, termed IP/EA-UCC3 and IP/EA-qUCCSD, are…

化学物理 · 物理学 2026-03-03 Yu Zhang , Junzi Liu

A new state specific correlation correction to configuration interaction singles (CIS) excitation energies is preseted using coupled cluster perturbation theory (CCPT). General expressions for CIS-CCPT are derived and expanded explicitly to…

化学物理 · 物理学 2015-06-19 Jason N. Byrd , Victor F. Lotrich , Rodney J. Bartlett

We extend the CIPSI-driven CC($P$;$Q$) methodology [K. Gururangan et al., J. Chem. Phys. 155 (2021) 174114], in which the leading higher-than-doubly excited determinants are identified using the selected configuration interaction (CI)…

化学物理 · 物理学 2026-02-24 Swati S. Priyadarsini , Karthik Gururangan , Piotr Piecuch

Wavefunctions restricted to electron pair states are promising models for strongly-correlated systems. Specifically, the pair Coupled Cluster Doubles (pCCD) ansatz allows us to accurately describe bond dissociation processes and…

强关联电子 · 物理学 2019-05-01 Katharina Boguslawski

We present a comprehensive theoretical study of the physical phenomena that determine the relative energies of the three of the lowest electronic states of each of the square-planar copper complexes $\cucl$, $\cunh$ and $\cuwater$, and…

强关联电子 · 物理学 2018-06-14 Emmanuel Giner , David Tew , Yann Garniron , Ali Alavi

We introduce an approach to improve single-reference coupled cluster theory in settings where the Aufbau determinant is absent from or plays only a small role in the true wave function. Using a de-excitation operator that can be efficiently…

化学物理 · 物理学 2024-07-03 Harrison Tuckman , Eric Neuscamman

In this work, we revisited the idea of using the coupled-cluster ground state formalism to target excited states. Our main focus was targeting doubly excited states and double core hole states. Typical equation-of-motion (EOM) approaches…

化学物理 · 物理学 2019-12-04 Joonho Lee , David W. Small , Martin Head-Gordon

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…

化学物理 · 物理学 2025-03-26 Megan Simons , Devin A. Matthews

Excited-state electronic structure in strongly correlated systems remains challenging due to the exponential scaling of the many-body Hilbert space and the difficulty of constructing systematically controlled active spaces. Building on the…

化学物理 · 物理学 2026-05-05 Annabelle Canestraight , Russell Miller , Libor Veis , Vojtech Vlcek

A novel approach to rapidly converging high-level coupled-cluster (CC) energetics in an automated fashion is proposed. The key idea is an adaptive selection of the excitation manifolds defining higher-than-two-body components of the cluster…

化学物理 · 物理学 2023-08-25 Karthik Gururangan , Piotr Piecuch
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