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We develop a method based on the relativistic coupled-cluster theory to incorporate a perturbative interaction to the no-pair Dirac-Coulomb atomic Hamiltonian. The method is general and suitable to incorporate any perturbation Hamiltonian…

Atomic Physics · Physics 2012-09-06 S. Chattopadhyay , B. K. Mani , D. Angom

We analyze the molecular electric dipole moments (PDMs) and static electric dipole polarizabilities of heteronuclear alkali dimers in their ground states by employing coupled-cluster theory, both in the non-relativistic and four-component…

Atomic Physics · Physics 2020-01-22 R. Mitra , V. S. Prasannaa , B. K. Sahoo

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…

Chemical Physics · Physics 2021-09-10 Antoine Marie , Fábris Kossoski , Pierre-François Loos

The molecular polarizability describes the tendency of a molecule to deform or polarize in response to an applied electric field. As such, this quantity governs key intra- and inter-molecular interactions such as induction and dispersion,…

Chemical Physics · Physics 2025-10-06 David M. Wilkins , Andrea Grisafi , Yang Yang , Ka Un Lao , Robert A. DiStasio , Michele Ceriotti

The ground X1{\Sigma}+ state potential energy curve (PEC) and dipole moment curve (DMC) of CO molecule have been revisited within the framework of the relativistic coupled-cluster approach, which incorporates non-perturbative single,…

A block-correlated coupled cluster (BCCC) method based on the generalized valence bond (GVB) wave function (GVB-BCCC in short) is proposed and implemented at the ab initio level, which represents an attractive multireference electronic…

Chemical Physics · Physics 2023-03-16 Qingchun Wang , Mingzhou Duan , Enhua Xu , Jingxiang Zou , Shuhua Li

With increasing demand for accurate calculation of isotope shifts of atomic systems for fundamental and nuclear structure research, an analytic energy derivative approach is presented in the relativistic coupled-cluster theory framework to…

The development of a quadratic unitary coupled-cluster singles and doubles (qUCCSD) based self-consistent polarization propagator method is reported. We present a simple strategy for truncating the commutator expansion of the UCC…

Chemical Physics · Physics 2024-06-19 Junzi Liu , Lan Cheng

We examine the contributions from triple excitation cluster operators in the relativistic coupled-cluster theory in atoms and ions. For this, we propose a tensor representation of the triple cluster operator. Based on this representaion and…

Atomic Physics · Physics 2015-03-19 B. K. Mani , Dilip Angom

We present the theory and implementation of a highly efficient relativistic third-order algebraic diagrammatic construction [ADC(3)] method based on a four-component (4c) Dirac-Coulomb (DC) Hamiltonian for the calculation of ionization…

Chemical Physics · Physics 2024-11-01 Sudipta Chakraborty , Tamoghna Mukhopadhyay , Malaya K. Nayak , Achintya Kumar Dutta

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…

Chemical Physics · Physics 2015-06-12 Michele Pavanello , Troy Van Voorhis , Lucas Visscher , Johannes Neugebauer

Accurately modeling chemical reactions at the atomistic level requires high-level electronic structure theory due to the presence of unpaired electrons and the need to properly describe bond breaking and making energetics. Commonly used…

The accurate calculation of excited state properties of interacting electrons in the condensed phase is an immense challenge in computational physics. Here, we use state-of-the-art equation-of-motion coupled-cluster theory with single and…

Chemical Physics · Physics 2019-07-10 Alan M. Lewis , Timothy C. Berkelbach

We consider evaluation of matrix elements with the coupled-cluster method. Such calculations formally involve infinite number of terms and we devise a method of partial summation (dressing) of the resulting series. Our formalism is built…

Atomic Physics · Physics 2009-11-10 Andrei Derevianko , Sergey Porsev

This article deals with the general implementation of 4-component spinor relativistic extended coupled cluster (ECC) method to calculate first order property of atoms and molecules in their open-shell ground state configuration. The…

Chemical Physics · Physics 2015-02-25 Sudip Sasmal , Himadri Pathak , Malaya K. Nayak , Nayana Vaval , Sourav Pal

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…

Chemical Physics · Physics 2025-03-26 Devin A. Matthews

Heavy polar diatomic molecules are currently among the most promising probes of fundamental physics. Constraining the electric dipole moment of the electron (eEDM), in order to explore physics beyond the Standard Model, requires a synergy…

Atomic Physics · Physics 2018-04-18 M Abe , V S Prasannaa , B P Das

We present a four-component relativistic unitary coupled cluster method for molecules. We have used commutator-based non-perturbative approximation using the ''Bernoulli expansion'' to derive an approximation to the relativistic unitary…

Chemical Physics · Physics 2024-03-06 Kamal Majee , Tamoghna Mukhopadhyay , Malaya K. Nayak , Achintya Kumar Dutta

We reveal limitations of several standard coupled-cluster (CC) methods with perturbation-theorybased noniterative or approximate iterative treatments of triple excitations when applied to thedetermination of highly accurate potential energy…

Chemical Physics · Physics 2021-10-04 Jan Schnabel , Lan Cheng , Andreas Köhn

Determination of nuclear moments for many nuclei relies on the computation of hyperfine constants, with theoretical uncertainties directly affecting the resulting uncertainties of the nuclear moments. In this work we improve the precision…

Atomic Physics · Physics 2022-01-05 S. G. Porsev , M. S. Safronova , M. G. Kozlov