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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 employ quantum Monte Carlo to obtain chemically accurate vertical and adiabatic excitation energies, and equilibrium excited-state structures for the small, yet challenging, formaldehyde and thioformaldehyde molecules. A key ingredient…

Computational Physics · Physics 2019-08-02 Monika Dash , Jonas Feldt , Saverio Moroni , Anthony Scemama , Claudia Filippi

In this work we describe the rank-reduced variant of the equation-of-motion coupled cluster theory with complete inclusion of single, double, and triple excitations. The advantage of the proposed formalism in comparison with the canonical…

Chemical Physics · Physics 2026-05-15 Piotr Michalak , Michał Lesiuk

The analytic gradient theory for both iterative and non-iterative coupled-cluster approximations that include connected quadruple excitations is presented. These methods include, in particular, CCSDT(Q), which is an analog of the well-known…

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

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

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…

An extensive analysis has been carried out of the performance of standard families of basis sets with the hierarchy of coupled cluster methods CC2, CCSD, CC3 and CCSDT in computing selected Oxygen, Carbon and Nitrogen K-edge (vertical) core…

Chemical Physics · Physics 2019-08-13 Johanna P. Carbone , Lan Cheng , Rolf H. Myhre , Devin Matthews , Henrik Koch , Sonia Coriani

We present an excited-state-specific coupled-cluster approach in which both the molecular orbitals and cluster amplitudes are optimized for an individual excited state. The theory is formulated via a pseudoprojection of the traditional…

Chemical Physics · Physics 2023-11-27 Harrison Tuckman , Eric Neuscamman

We present a novel and cost-effective approach of using a second similarity transformation of the Hamiltonian to include the missing higher-order terms in the second-order approximate coupled cluster singles and doubles (CC2) model. The…

Chemical Physics · Physics 2022-01-26 Soumi Haldar , Achintya Kumar Dutta

The quantum equation-of-motion (qEOM) method with singles and doubles has been suggested to study electronically excited states while it fails to predict the excitation energies dominated by double excitations. In this work, we present an…

Quantum Physics · Physics 2024-06-18 Yuhan Zheng , Jie Liu , Zhenyu Li , Jinlong Yang

The reformulated coupled-cluster method (CCM), in which average many-body potentials are introduced, provides a useful framework to organize numerous terms appearing in CCM equations, which enables us to clarify the structure of the CCM…

Nuclear Theory · Physics 2015-06-05 M. Kohno , R. Okamoto

We report ground- and excited-state dipole moments and oscillator strengths (computed in different ``gauges'' or representations) of full configuration interaction (FCI) quality using the selected configuration interaction method known as…

Polarizable Quantum Mechanics/Molecular Mechanics (QM/MM) approaches based on fluctuating charges and dipoles (QM/FQ(F$\mu$)) are formulated within the state-specific Vertical Excitation Model (VEM) to compute vertical excitation energies…

Chemical Physics · Physics 2025-11-05 Chiara Sepali , Piero Lafiosca , Linda Goletto , Tommaso Giovannini , Chiara Cappelli

Quantum chemistry simulations offer a cost-effective way for computational design of BODIPY photosensitizers with potential use in photodynamic therapy (PDT). However, accurate predictions of photophysical properties, such as excitation…

A major difficulty in quantum simulation is the adequate treatment of a large collection of entangled particles, synonymous with electron correlation in electronic structure theory, with coupled cluster (CC) theory being the leading…

Chemical Physics · Physics 2024-06-06 Zachary W. Windom , Daniel Claudino , Rodney J. Bartlett

While the periodic equation-of-motion coupled-cluster (EOM-CC) method promises systematic improvement of electronic band gap calculations in solids, its practical application at the singles and doubles level (EOM-CCSD) is hindered by severe…

Downfolding coupled cluster (CC) techniques are powerful tools for reducing the dimensionality of many-body quantum problems. This work investigates how ground-state downfolding formalisms can target excited states using non-Aufbau…

Chemical Physics · Physics 2023-10-24 Nicholas P. Bauman

We introduce and benchmark a systematically improvable route for excited-state calculations, state-specific configuration interaction ($\Delta$CI), \alert{which is a particular realization of multiconfigurational self-consistent field and…

Chemical Physics · Physics 2023-08-31 Fábris Kossoski , Pierre-François Loos

The Trotterized Unitary Coupled Cluster Single and Double (UCCSD) ansatz has recently attracted interest due to its use in Variation Quantum Eigensolver (VQE) molecular simulations on quantum computers. However, when the size of molecules…

Chemical Physics · Physics 2023-05-29 Mohammad Haidar , Marko J. Rančić , Yvon Maday , Jean-Philip Piquemal

Quantum Monte Carlo (QMC) is a stochastic method which has been particularly successful for ground-state electronic structure calculations but mostly unexplored for the computation of excited-state energies. Here, we show that, within a…

Chemical Physics · Physics 2018-08-09 Anthony Scemama , Anouar Benali , Denis Jacquemin , Michel Caffarel , Pierre-François Loos