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The coupled cluster iteration scheme for determining the cluster amplitudes involves a set of nonlinearly coupled difference equations. In the space spanned by the amplitudes, the set of equations are analysed as a multivariate…

The performance of quantum algorithms for ground-state energy estimation is directly impacted by the quality of the initial state, where quality is traditionally defined in terms of the overlap of the input state with the target state. An…

We investigate the use of orbital-optimized references in conjunction with single-reference coupled-cluster theory with single and double substitutions (CCSD) for the study of core excitations and ionizations of 18 small organic molecules,…

Simulating molecules using the Variational Quantum Eigensolver method is one of the promising applications for NISQ-era quantum computers. Designing an efficient ansatz to represent the electronic wave function is crucial in such…

Chemical Physics · Physics 2022-05-09 Dmitry A. Fedorov , Yuri Alexeev , Stephen K. Gray , Matthew Otten

Multireference systems are usually challenging to investigate using ab initio methods as they require an accurate description of static electron correlation. The urgency of developing similar approaches is even more pressing when molecules…

Chemical Physics · Physics 2025-06-11 Riccardo Alessandro , Matteo Castagnola , Henrik Koch , Enrico Ronca

We consider the rank-reduced coupled-cluster theory with single and double excitations (RR-CCSD) introduced recently [Parrish \emph{et al.}, J. Chem. Phys. {\bf 150}, 164118 (2019)]. The main feature of this method is the decomposed form of…

Chemical Physics · Physics 2022-02-21 Michał Lesiuk

Inspired by our earlier semi-stochastic work aimed at converging high-level coupled-cluster (CC) energetics [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017); J. Chem. Phys. 154, 124103 (2021)], we propose a novel…

Chemical Physics · Physics 2022-10-06 Karthik Gururangan , J. Emiliano Deustua , Jun Shen , Piotr Piecuch

The complete active space self-consistent field (CASSCF) method is the principal approach employed for studying strongly correlated systems. However, exact CASSCF can only be performed on small active spaces of ~20 electrons in ~20 orbitals…

Computational Physics · Physics 2021-12-22 Daniel S. Levine , Diptarka Hait , Norm M. Tubman , Susi Lehtola , K. Birgitta Whaley , Martin Head-Gordon

Even when starting with a very poor initial guess, the iterative configuration interaction (iCI) approach can converge from above to full CI very quickly by constructing and diagonalizing a small Hamiltonian matrix at each…

Chemical Physics · Physics 2020-01-07 Ning Zhang , Wenjian Liu , Mark R. Hoffmann

While limited coupled cluster theory is \textit{formally} nonvariational, it is not broadly appreciated whether this is a major issue \textit{in practice}. We carried out a detailed comparison with \textit{de facto} full CI energies for a…

Chemical Physics · Physics 2024-10-03 Jan M. L. Martin , Emmanouil Semidalas

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

In the last decade, the quantum chemical version of the density matrix renormalization group (DMRG) method has established itself as the method of choice for calculations of strongly correlated molecular systems. Despite its favourable…

Chemical Physics · Physics 2016-11-15 Libor Veis , Andrej Antalík , Jiří Brabec , Frank Neese , Örs Legeza , Jiří Pittner

Tailored coupled cluster theory represents a computationally inexpensive way to describe static and dynamical electron correlation effects. In this work, we scrutinize the performance of various tailored coupled cluster methods externally…

Chemical Physics · Physics 2021-03-24 Aleksandra Leszczyk , Mihály Máté , Örs Legeza , Katharina Boguslawski

We report an efficient algorithm using density fitting for the relativistic complete active space self-consistent field (CASSCF) method, which is significantly more stable than the algorithm previously reported by one of the authors [J. E.…

Chemical Physics · Physics 2018-08-01 Ryan D. Reynolds , Takeshi Yanai , Toru Shiozaki

Coupled cluster theory is a vital cornerstone of electronic structure theory and is being applied to ever-larger systems. Stochastic approaches to quantum chemistry have grown in importance and offer compelling advantages over traditional…

We present the formulation and implementation of the integral- and intermediate-screened coupled-cluster method (ISSCC). The IISCC method gives a simple and rigorous integral and intermediate screening (IIS) of the coupled-cluster method…

Chemical Physics · Physics 2016-11-10 L. K. Sørensen

In this work, we combine the many-body formulation of the internally contracted multireference coupled cluster (ic-MRCC) method with Evangelista's multireference formulation of the driven similarity renormalization group (DSRG). The DSRG…

Chemical Physics · Physics 2025-03-04 Robin Feldmann , Markus Reiher

Doubly occupied configuration interaction (DOCI) with optimized orbitals often accurately describes strong correlations while working in a Hilbert space much smaller than that needed for full configuration interaction. However, the scaling…

Chemical Physics · Physics 2016-02-25 Thomas M. Henderson , Ireneusz W. Bulik , Tamar Stein , Gustavo E. Scuseria

The coupled cluster method is considered a gold standard in quantum chemistry, reliably giving energies that are exact within chemical accuracy (1.6 mHartree). However, even in the CCSD approximation, where the cluster operator is truncated…

Chemical Physics · Physics 2023-03-10 Simon Elias Schrader , Simen Kvaal

The development of multireference coupled cluster (MRCC) techniques has remained an open area of study in electronic structure theory for decades due to the inherent complexity of expressing a multi-configurational wavefunction in the…

Chemical Physics · Physics 2023-05-24 Maria-Andreea Filip , Alex J. W. Thom