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The (T) and [T] perturbative corrections are derived for multicomponent coupled-cluster theory with single and double excitations (CCSD). Benchmarking shows that multicomponent CCSD methods that include the perturbative corrections are more…

化学物理 · 物理学 2022-07-01 Dylan Fowler , Kurt R. Brorsen

Multicomponent systems are defined as chemical systems that require a quantum mechanical description of two or more different types of particles. Non-Born-Oppenheimer electron-nuclear interactions in molecules, electron-hole interactions in…

化学物理 · 物理学 2015-10-21 Benjamin H. Ellis , Somil Aggarwal , Arindam Chakraborty

Fourth-order many-body corrections to matrix elements for atoms with one valence electron are derived. The obtained diagrams are classified using coupled-cluster-inspired separation into contributions from n-particle excitations from the…

原子物理 · 物理学 2009-11-07 Andrei Derevianko , Erik D. Emmons

We investigate the role of the electron correlation effects in the calculations of the electric dipole polarizabilities (\alpha) of elements belonging to three different groups of periodic table. To understand the propagation of the…

原子物理 · 物理学 2014-05-21 Yashpal Singh , B. K. Sahoo

Treating electron correlation more accurately and efficiently is at the heart of the development of electronic structure methods. In the present work, we explore the use of stochastic approaches to evaluate high-order electron correlation…

化学物理 · 物理学 2020-01-29 Zhendong Li

In this work, we introduce a correction to the unitary coupled cluster method with single and double excitations (UCCSD) that incorporates the effects of missing triple excitations through a treatment that is correct through fifth-order in…

化学物理 · 物理学 2025-09-08 Zachary W. Windom , Daniel Claudino

The accurate description of nuclear quantum effects, such as zero-point energy, is important for modeling a wide range of chemical and biological processes. Within the nuclear-electronic orbital (NEO) approach, such effects are incorporated…

化学物理 · 物理学 2022-09-07 Fabijan Pavošević , Sharon Hammes-Schiffer

A major difficulty in quantum simulation is the adequate treatment of a large collection of entangled particles, synonymous with electron correlation in electronic structure theory, with coupled cluster (CC) theory being the leading…

化学物理 · 物理学 2024-06-06 Zachary W. Windom , Daniel Claudino , Rodney J. Bartlett

Coupled-cluster theory with single, double, and perturbative triple excitations (CCSD(T)) -- often considered the "gold standard" of main-group quantum chemistry -- is inapplicable to three-dimensional metals due to an infrared divergence,…

材料科学 · 物理学 2023-03-21 Verena A. Neufeld , Timothy C. Berkelbach

A second-order many-body perturbation correction to the relativistic Dirac-Hartree-Fock energy is evaluated stochastically by integrating 13-dimensional products of four-component spinors and Coulomb potentials. The integration in the real…

量子物理 · 物理学 2022-06-16 J. César Cruz , Jorge Garza , Takeshi Yanai , So Hirata

A number of iterative and perturbative approximations to the full equation-of-motion coupled cluster method with single, double, and triple excitations (EOM-CCSDT) are evaluated in the context of calculating the K-edge core-excitation and…

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

The relative energies of different phases or polymorphs of molecular solids can be small, less than a kiloJoule/mol. Reliable description of such energy differences requires high quality treatment of electron correlations, typically beyond…

化学物理 · 物理学 2024-02-19 Khanh Ngoc Pham , Marcin Modrzejewski , Jiří Klimeš

Multicomponent methods seek to treat select nuclei, typically protons, fully quantum mechanically and equivalent to the electrons of a chemical system. In such methods, it is well known that due to the neglect of electron-proton…

化学物理 · 物理学 2020-12-21 O. Jonathan Fajen , Kurt R. Brorsen

We report a complete implementation of the coupled-cluster method with single, double, and triple excitations (CCSDT) where tensor decompositions are used to reduce its scaling and overall computational costs. For the decomposition of the…

化学物理 · 物理学 2020-02-20 Michał Lesiuk

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

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.…

材料科学 · 物理学 2021-06-16 James M. Callahan , Malte F. Lange , Timothy C. Berkelbach

Coupled cluster methods based exclusively on double excitations are comparatively "cheap" and interesting model chemistries, as they are typically able to capture the bulk of the dynamical electron correlation effects. The trade-off in such…

量子物理 · 物理学 2024-06-14 Zachary W. Windom , Daniel Claudino , Rodney J. Bartlett

A practical high-accuracy relativistic method of atomic structure calculations for univalent atoms is presented. The method is rooted in the coupled-cluster formalism and includes non-perturbative treatment of single and double excitations…

原子物理 · 物理学 2009-11-11 Sergey G. Porsev , Andrei Derevianko

We present a perturbative triples correction to the relativistic quadratic unitary coupled cluster singles and doubles (qUCCSD) method, denoted as qUCCSD[T]. The method builds upon the Hermitian structure of the unitary ansatz and employs a…

化学物理 · 物理学 2025-10-08 Kamal Majee , Ján Šimunek , Jozef Noga , Achintya Kumar Dutta

We investigate the accuracy of a number of wavefunction based methods at the heart of quantum chemistry for metallic systems. Using Hartree-Fock as a reference, perturbative (M{\o}ller-Plesset, MP) and coupled cluster (CC) theories are used…

化学物理 · 物理学 2013-10-24 James J. Shepherd , Andreas Grüneis
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