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We present an excited-state-specific coupled-cluster approach in which both the molecular orbitals and cluster amplitudes are optimized for an individual excited state. The theory is formulated via a pseudoprojection of the traditional…

化学物理 · 物理学 2023-11-27 Harrison Tuckman , Eric Neuscamman

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

A new perturbative approach to canonical equation-of-motion coupled-cluster theory is presented using coupled-cluster perturbation theory. A second-order M{\o}ller-Plesset partitioning of the Hamiltonian is used to obtain the well known…

化学物理 · 物理学 2015-07-09 Jason N. Byrd , Varun Rishi , Ajith Perera , Rodney J. Bartlett

Intermolecular charge-transfer (xCT) excited states important for various practical applications are challenging for many standard computational methods. It is highly desirable to have an affordable method that can treat xCT states…

化学物理 · 物理学 2024-11-04 Nhan Tri Tran , Lan Nguyen Tran

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…

化学物理 · 物理学 2022-01-26 Soumi Haldar , Achintya Kumar Dutta

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

We show that by working in a basis similar to that of the natural transition orbitals and using a modified zeroth order Hamiltonian, the cost of a recently-introduced perturbative correction to excited state mean field theory can be reduced…

化学物理 · 物理学 2020-09-03 Rachel Clune , Jacqueline A. R. Shea , Eric Neuscamman

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…

We present a study of the two dimensional circular quantum dot model Hamiltonian using a range of quantum chemical ab initio methods. Ground and excited state energies are computed on different levels of perturbation theories including the…

化学物理 · 物理学 2022-03-23 Faruk Salihbegović , Alejandro Gallo , Andreas Grüneis

A microscopic description of nuclei is important to understand the nuclear shell-model from fundamental principles. This is difficult to achieve for more than the lightest nuclei without an effective approximation scheme. The purpose of…

核理论 · 物理学 2013-08-19 Gustav R. Jansen

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…

化学物理 · 物理学 2023-09-18 Loïc Halbert , Andre Severo Pereira Gomes

Quantum--Mechanical methods that are both computationally fast and accurate are not yet available for electronic excitations having charge transfer character. In this work, we present a significant step forward towards this goal for those…

化学物理 · 物理学 2015-06-12 Michele Pavanello , Troy Van Voorhis , Lucas Visscher , Johannes Neugebauer

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

In the framework of the computational determination of highly-accurate vertical excitation energies in small organic compounds, we explore the possibilities offered by the equation-of-motion formalism relying on the approximate fourth-order…

We present a first principles strategy for developing state-specific density functional approximations for excited states. We first clarify why approaches based on conventional ground state approximations miss density-driven correlations,…

化学物理 · 物理学 2025-06-09 Tim Gould , Stephen G Dale , Leeor Kronik , Stefano Pittalis

We explore the possibility of calculating electronic excited states by using perturbation theory along a range-separated adiabatic connection. Starting from the energies of a partially interacting Hamiltonian, a first-order correction is…

化学物理 · 物理学 2014-12-15 Elisa Rebolini , Julien Toulouse , Andrew M. Teale , Trygve Helgaker , Andreas Savin

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,…

化学物理 · 物理学 2026-03-16 Jonathan H. Fetherolf , Fabijan Pavošević , Sharon Hammes-Schiffer

Time-dependent response theories are foundational to the development of algorithms that determine quantum properties of electronic excited states of molecules and periodic systems. They are employed in wave-function, density-functional, and…

化学物理 · 物理学 2022-11-23 Martín A. Mosquera

The similarity transformed equation of motion coupled cluster (STEOM-CC) method is benchmarked against CC3 and EOM-CCSDT-3 for a large test set of valence excited states of organic molecules studied by Schreiber et al. [M. Schreiber, M.R.…

化学物理 · 物理学 2018-01-09 J. Sous , P. Goel , M. Nooijen

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
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