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We introduce a new equation-of-motion coupled-cluster method based on a pair coupled-cluster doubles (pCCD) reference, termed frozen-pair EOM-CCSD (EOM-fpCCSD). This approach combines the computational efficiency of the pCCD ansatz with a…

Chemical Physics · Physics 2026-05-06 Katharina Boguslawski , Paweł Tecmer

Valence excitation spectra are computed for all deep-center silicon-vacancy defect types in 3C, 4H, and 6H silicon carbide (SiC) and comparisons are made with literature photoluminescence measurements. Nuclear geometries surrounding the…

Chemical Physics · Physics 2018-03-14 Jesse J. Lutz , Xiaofeng F. Duan , Larry W. Burggraf

We present an implementation of equation of motion coupled-cluster singles and doubles (EOM-CCSD) theory using periodic boundary conditions and a plane wave basis set. Our implementation of EOM-CCSD theory is applied to study $F$-centers in…

Materials Science · Physics 2021-02-09 Alejandro Gallo , Felix Hummel , Andreas Irmler , Andreas Grüneis

We present the theoretical framework, implementation, and benchmark results for a reduced-cost relativistic equation-of-motion coupled cluster singles and doubles (EOM-CCSD) method based on state-specific frozen natural spinors (SS-FNS). In…

Reliable computational methodologies and basis sets for modeling x-ray spectra are essential for extracting and interpreting electronic and structural information from experimental x-ray spectra. In particular, the trade-off between…

Chemical Physics · Physics 2025-03-26 Alexis A. A. Delgado , Devin A. Matthews

We formulate and implement the core-valence separated multireference equation-of-motion driven similarity renormalization group method (CVS-IP-EOM-DSRG) for simulating X-ray photoelectron spectra (XPS) of strongly correlated molecular…

Chemical Physics · Physics 2025-09-29 Shuhang Li , Zijun Zhao , Francesco A. Evangelista

The Coupled Cluster (CC) method is used to compute the electronic correlation energy in atoms and molecules and often leads to highly accurate results. However, due to its single-reference nature, standard CC in its projected form fails to…

Quantum subspace diagonalization (QSD) methods are quantum-classical hybrid methods, commonly used to find ground and excited state energies by projecting the Hamiltonian to a smaller subspace. In applying these, the choice of subspace…

Quantum Physics · Physics 2022-09-23 Akhil Francis , Anjali A. Agrawal , Jack H. Howard , Efekan Kökcü , A. F. Kemper

Problems in quantum chemical simulations, especially achieving accurate excited-state potential energy surfaces, are among the primary applications to achieve quantum utility. On near-term quantum hardware, variants of the variational…

A reduced-complexity variant of equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) method is formulated in terms of state-averaged excited state pair natural orbitals (PNO) designed to describe manifolds of excited states.…

Chemical Physics · Physics 2020-06-09 Chong Peng , Marjory C. Clement , Edward F. Valeev

Near-term quantum computers are expected to facilitate material and chemical research through accurate molecular simulations. Several developments have already shown that accurate ground-state energies for small molecules can be evaluated…

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…

Chemical Physics · Physics 2024-06-13 Yann Damour , Anthony Scemama , Denis Jacquemin , Fábris Kossoski , Pierre-François Loos

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…

Chemical Physics · Physics 2019-12-04 Joonho Lee , David W. Small , Martin Head-Gordon

We present an implementation of equation-of-motion oscillator strengths for the multilevel CCSD (MLCCSD) model where CCS is used as the lower level method (CCS/CCSD). In this model, the double excitations of the cluster operator are…

Chemical Physics · Physics 2020-09-21 Sarai D. Folkestad , Henrik Koch

Developing efficient path integral (PI) methods for atomistic simulations of vibrational spectra in heterogeneous condensed phases and interfaces has long been a challenging task. Here, we present the h-CMD method, short for hybrid centroid…

Chemical Physics · Physics 2025-05-08 Dil K. Limbu , Nathan London , Md Omar Faruque , Mohammad R. Momeni

We present our successful implementation of the quantum electrodynamics coupled-cluster method with single and double excitations (QED-CCSD) for electronic and bosonic amplitudes, covering both individual and mixed excitation processes…

Quantum Physics · Physics 2024-09-12 Himadri Pathak , Nicholas P. Bauman , Ajay Panyala , Karol Kowalski

Time-dependent equation-of-motion coupled cluster (TD-EOM-CC) is used to simulate impulsive stimulated x-ray Raman scattering (ISXRS) of ultrashort laser pulses by neon, carbon monoxide, pyrrole, and p-aminophenol. The TD-EOM-CC equations…

Chemical Physics · Physics 2023-10-10 Alice Balbi , Andreas S. Skeidsvoll , Henrik Koch

Simulations of laser-induced electron dynamics in a molecular system are performed using time-dependent (TD) equation-of-motion (EOM) coupled-cluster (CC) theory. The target system has been chosen to highlight potential shortcomings of…

Chemical Physics · Physics 2023-08-09 Stephen H. Yuwono , Brandon C. Cooper , Tianyuan Zhang , Xiaosong Li , A. Eugene DePrince

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…

Chemical Physics · Physics 2019-05-01 Katharina Boguslawski

Using the Wentzel-Kramers-Brillouin method, we derive a modified form of the Thomas-Fermi approximation to electron density. This new result enables us to calculate the details of the self-consistent ion cores, as well as the ionization…

Materials Science · Physics 2009-02-23 Gregory C. Dente , Michael L. Tilton