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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…

Chemical Physics · Physics 2015-07-09 Jason N. Byrd , Varun Rishi , Ajith Perera , Rodney J. Bartlett

We present an implementation of relativistic ionization-potential (IP) equation-of-motion coupled-cluster (EOMCC) with up to 3-hole--2-particle (3h2p) excitations that makes use of the molecular mean-field exact two-component (mmfX2C)…

Chemical Physics · Physics 2025-01-10 Stephen H. Yuwono , Run R. Li , Tianyuan Zhang , Xiaosong Li , A. Eugene DePrince

We present an implementation for the use of Cholesky decomposition (CD) of two-electron integrals within the spin-free Dirac-Coulomb (SFDC) scheme that enables to perform high-accuracy coupled-cluster (CC) calculations at costs almost…

Chemical Physics · Physics 2024-07-02 Tereza Uhlířová , Davide Cianchino , Tommaso Nottoli , Filippo Lipparini , Jürgen Gauss

The double ionization potential (DIP) equation-of-motion (EOM) coupled-cluster (CC) method with a full treatment of 4-hole-2-particle (4$h$-2$p$) correlations and triply excited clusters, abbreviated as DIP-EOMCCSDT(4$h$-2$p$), and its…

Chemical Physics · Physics 2025-02-12 Karthik Gururangan , Achintya Kumar Dutta , Piotr Piecuch

We report the general implementation of the relativistic equation-of-motion coupled-cluster method to calculate double ionization spectra (DI-EOMCC) of atomic and molecular systems. As a first application, this method is employed to…

Atomic Physics · Physics 2014-08-25 Himadri Pathak , Aryya Ghosh , B. K. Sahoo , B. P. Das , Nayana Vaval , Sourav Pal

We report our successful implementation of the full fledged relativistic equation of motion coupled cluster (EOMCC) method. This method is employed to compute the principal ionization potentials (IPs) of closed-shell rare gas atoms, He-like…

Atomic Physics · Physics 2014-04-24 Himadri Pathak , B. K. Sahoo , B. P. Das , Nayana Vaval , Sourav Pal

We report the implementation of equation-of-motion coupled-cluster (EOMCC) method in the four-component relativistic framework with the spherical atomic potential to generate the excited states from a closed-shell atomic configuration. This…

Atomic Physics · Physics 2015-06-19 D. K. Nandy , Yashpal Singh , B. K. Sahoo

We have presented the theory, implementation, and benchmark results for the one-electronic variant of spin-free exact two-component (SFX2C1e) linear response coupled cluster (LRCCSD) theory for static and dynamic polarizabilities of atoms…

Chemical Physics · Physics 2024-05-31 Sudipta Chakraborty , Tamoghna Mukhopadhyay , Achintya Kumar Dutta

We present the theory, implementation, and benchmark results for a frozen natural spinors-based lower scaling four-component relativistic coupled cluster method. The natural spinors are obtained by diagonalizing the one-body reduced density…

Chemical Physics · Physics 2022-06-15 Somesh Chamoli , Kshitijkumar Surjuse , Malaya K. Nayak , Achintya Kumar Dutta

An approximate relativistic two-component Hamiltonian for use in molecular electronic structure calculations is derived in the form of a sum of fixed atom-centered kinetic and spin-orbit operators added to the non-relativistic Hamiltonian.…

Chemical Physics · Physics 2019-02-13 Dimitri N. Laikov

We have implemented relativistic formulations of DIP-EOMCCSD and DIP-EOMCCSDT within the 1eX2C and DC-, DCG-, and DCB-X2C frameworks. Direct comparisons against full 4c-DIP-EOMCCSD calculations show excellent agreement with…

We introduce the electron attachment equation-of-motion pair coupled cluster doubles (EA-EOM-pCCD) ansatz, which allows us to inexpensively compute electron affinities, energies of unoccupied orbitals, and electron attachment spectra. We…

Chemical Physics · Physics 2024-06-24 Marta Gałyńska , Paweł Tecmer , Katharina Bogusławski

We present a relativistic third-order algebraic diagrammatic construction (ADC(3)) approach for calculating double ionization potentials (DIPs). By employing the exact two-component atomic mean-field (X2CAMF) Hamiltonian in combination with…

Chemical Physics · Physics 2025-10-08 Sujan Mandal , Achintya Kumar Dutta

We present a reduced-cost equation-of-motion coupled-cluster method for excited states, built on a new state-specific frozen natural orbital (SS-FNO) framework. This approach enables systematic and controllable truncation of the virtual…

Chemical Physics · Physics 2025-07-24 Amrita Manna , Achintya Kumar Dutta

A novel implementation of the coupled-cluster singles and doubles (CCSD) approach is presented that is specifically tailored for the treatment of large, symmetric systems. It fully exploits Abelian point-group symmetry and the use of the…

Chemical Physics · Physics 2023-12-07 Tommaso Nottoli , Jürgen Gauss , Filippo Lipparini

In the present work we report an implementation of the rank-reduced equation-of-motion coupled cluster method with approximate triple excitations (RR-EOM-CC3). The proposed variant relies on tensor decomposition techniques in order to…

Chemical Physics · Physics 2025-08-26 Piotr Michalak , Michał Lesiuk

The projection-based quantum embedding method is applied to electronically excited states of valence, Rydberg, and charge-transfer character, valence- and core-ionized states, as well as bound and temporary radical anions. We embed…

Chemical Physics · Physics 2021-06-10 Valentina Parravicini , Thomas-C. Jagau

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

We present a novel and efficient implementation of coupled-cluster with singles and doubles (CCSD) analytic gradients that combines the Cholesky decomposition (CD) of electron-repulsion integrals with the exploitation of Abelian point-group…

Chemical Physics · Physics 2025-12-29 Luca Melega , Tommaso Nottoli , Jürgen Gauss , Filippo Lipparini

We report an implementation of the core-valence separation approach to the 4-component relativistic Hamiltonian based equation-of-motion coupled-cluster with singles and doubles theory (CVS-EOM-CCSD), for the calculation of relativistic…