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In the framework of the computational determination of highly-accurate vertical excitation energies in small organic compounds, we explore the possibilities offered by the equation-of-motion formalism relying on the approximate fourth-order…

We introduce a multimodel approach to solve coupled cluster equations, employing a quasi Newton algorithm for the ground state and an Olsen algorithm for the excited states. In these algorithms, both of which can be viewed as Newton…

Chemical Physics · Physics 2020-07-15 Eirik F. Kjønstad , Sarai D. Folkestad , Henrik Koch

Quantum Phase Estimation (QPE), the quantum algorithm for estimating eigenvalues of a given Hermitian matrix and preparing its eigenvectors, is considered the most promising approach to finding the ground states and their energies of…

We report the first study using active-orbital-based and adaptive CC($P$;$Q$) approaches to describe excited electronic states. These CC($P$;$Q$) methodologies are applied, alongside their completely renormalized (CR) coupled-cluster (CC)…

Chemical Physics · Physics 2025-01-08 Karthik Gururangan , Jun Shen , Piotr Piecuch

Since in coupled-cluster (CC) theory ground-state and excitation energies are eigenvalues of a non-Hermitian matrix, these energies can in principle take on complex values. In this paper we discuss the appearance of complex energy values in…

Chemical Physics · Physics 2022-01-12 Simon Thomas , Florian Hampe , Stella Stopkowicz , Jürgen Gauss

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…

We propose a state-specific orbital optimization scheme for improving the accuracy of excited states of the electronic structure Hamiltonian for the use on near-term quantum computers, which can be combined with any overlap-based…

Quantum Physics · Physics 2025-10-16 Guorui Zhu , Joel Bierman , Jianfeng Lu , Yingzhou Li

We present a formulation of excited state mean-field theory in which the derivatives with respect to the wave function parameters needed for wave function optimization (not to be confused with nuclear derivatives) are expressed analytically…

Chemical Physics · Physics 2020-06-24 Luning Zhao , Eric Neuscamman

We report the first investigation of the performance of EOM-CC4 -- an approximate equation-of-motion coupled-cluster model which includes iterative quadruple excitations -- for vertical excitation energies in molecular systems. By…

Chemical Physics · Physics 2021-06-14 Pierre-François Loos , Devin A. Matthews , Filippo Lipparini , Denis Jacquemin

A new method that accurately describes strongly correlated states and captures dynamical correlation is presented. It is derived as a modification of coupled-cluster theory with single and double excitations (CCSD) through consideration of…

Chemical Physics · Physics 2013-07-15 Daniel Kats , Frederick R. Manby

We report the implementation of a cost-effective approximation method within the framework of time-dependent optimized coupled-cluster (TD-OCC) method [J. Chem. Phys. 148, 051101 (2018)] for real-time simulations of intense laser-driven…

Chemical Physics · Physics 2020-04-22 Himadri Pathak , Takeshi Sato , Kenichi L. Ishikawa

Adapting a veritable many-body method to a system of non-interacting particles (NIP), while being trivial from a physical point of view, can be of interest with regard to methodological aspects. In this article we study the NIP versions of…

Chemical Physics · Physics 2023-11-07 Jochen Schirmer

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

Density functional theory (DFT) based modeling of electronic excited states is of importance for investigation of the photophysical/photochemical properties and spectroscopic characterization of large systems. The widely used linear…

Chemical Physics · Physics 2021-05-11 Diptarka Hait , Martin Head-Gordon

A central difficulty of state-specific Multi-Reference Coupled Cluster (MR-CC) formalisms concerns the definition of the amplitudes of the single and double excitation operators appearing in the exponential wave operator. If the reference…

Chemical Physics · Physics 2017-04-20 Yann Garniron , Emmanuel Giner , Jean-Paul Malrieu , Anthony Scemama

Recent work from our research group has demonstrated that symmetry-projected Hartree--Fock (HF) methods provide a compact representation of molecular ground state wavefunctions based on a superposition of non-orthogonal Slater determinants.…

Chemical Physics · Physics 2015-06-17 Carlos A. Jiménez-Hoyos , R. Rodríguez-Guzmán , Gustavo E. Scuseria

The dipole moment is a crucial molecular property linked to a molecular system's bond polarity and overall electronic structure. To that end, the electronic dipole moment, which results from the electron density of a system, is often used…

Variational calculations of excited electronic states are carried out by finding saddle points on the surface that describes how the energy of the system varies as a function of the electronic degrees of freedom. This approach has several…

Chemical Physics · Physics 2023-02-15 Yorick L. A. Schmerwitz , Gianluca Levi , Hannes Jónsson

Numerous numerical studies have shown that geminal-based methods are a promising direction to model strongly correlated systems with low computational costs. Several strategies have been introduced to capture the missing dynamical…

Chemical Physics · Physics 2023-03-22 Artur Nowak , Katharina Boguslawski

We systematically investigate the calculation of excited states in quantum chemistry using auxiliary field quantum Monte Carlo (AFQMC). Symmetry allows targeting of the lowest triplet excited states in AFQMC based on restricted open-shell…

Chemical Physics · Physics 2025-09-16 Ankit Mahajan , Sandeep Sharma , Shiwei Zhang , David R. Reichman
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