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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 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

A set of density functionals coming from different rungs on Jacob's ladder are employed to evaluate the electronic excited states of three Ru(II) complexes. While most studies on the performance of density functionals compare the vertical…

State-specific approximations can provide an accurate representation of challenging electronic excitations by enabling relaxation of the electron density. While state-specific wave functions are known to be local minima or saddle points of…

Chemical Physics · Physics 2022-01-06 Hugh G. A. Burton

Determining quantum excited states is crucial across physics and chemistry but presents significant challenges for variational methods, primarily due to the need to enforce orthogonality to lower-energy states, often requiring…

Quantum Physics · Physics 2025-05-01 Shi-Xin Zhang , Lei Wang

We perform excited-state variational Monte Carlo and diffusion Monte Carlo calculations using a simple and efficient wave function ansatz. This ansatz follows the recent variation-after-response formalism, accurately approximating a…

Strongly Correlated Electrons · Physics 2018-12-24 Nick S. Blunt , Eric Neuscamman

We demonstrate that, if a truncated expansion of a wave function is small, then the standard excited states computational method, of optimizing one root of a secular equation, may lead to an incorrect wave function - despite the correct…

Atomic Physics · Physics 2016-12-21 N. C. Bacalis , Z. Xiong , J. Zang , D. Karaoulanis

The computation of small concise and comprehensible excited state wave functions is needed because many electronic processes occur in excited states. But since the excited energies are saddle points in the Hilbert space of wave functions,…

Chemical Physics · Physics 2016-02-04 Naoum C. Bacalis

We introduce an approach to improve single-reference coupled cluster theory in settings where the Aufbau determinant is absent from or plays only a small role in the true wave function. Using a de-excitation operator that can be efficiently…

Chemical Physics · Physics 2024-07-03 Harrison Tuckman , Eric Neuscamman

It has been well established that the Jastrow correlation factor can effectively capture the electron correlation effects, and thus, the efficient optimization of the many-body wave function including the Jastrow correlation factor is of…

Atomic Physics · Physics 2023-09-12 Masayuki Ochi

We extend our hybrid linear-method/accelerated-descent variational Monte Carlo optimization approach to excited states and investigate its efficacy in double excitations. In addition to showing a superior statistical efficiency when…

Chemical Physics · Physics 2022-02-24 Leon Otis , Isaac M. Craig , Eric Neuscamman

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 present a discussion of recent progress in excited-state-specific quantum chemistry and quantum Monte Carlo alongside a demonstration of how a combination of methods from these two fields can offer reliably accurate excited state…

Chemical Physics · Physics 2023-02-07 Leon Otis , Eric Neuscamman

A systematic method for determining correlated wavefunctions of extended systems in the ground and excited states is presented. It allows to fully exploit the power of quantum-chemical programs designed for correlation calculations of…

Other Condensed Matter · Physics 2007-05-23 V. Bezugly

Recently developed neural network-based wave function methods are capable of achieving state-of-the-art results for finding the ground state in real space. In this work, a neural network-based method is used to compute excited states. We…

Computational Physics · Physics 2021-10-04 Yimeng Min

This work presents a series of highly-accurate excited-state properties obtained using high-order coupled-cluster (CC) calculations performed with a series of diffuse containing basis sets, as well as extensive comparisons with experimental…

Chemical Physics · Physics 2021-06-14 Amara Chrayteh , Aymeric Blondel , Pierre-François Loos , Denis Jacquemin

We present a multi-reference configuration mixing scheme for describing ground and excited states, with well defined spin and space group symmetry quantum numbers, of the one-dimensional Hubbard model with nearest-neighbor hopping and…

Strongly Correlated Electrons · Physics 2013-06-28 R. Rodríguez-Guzmán , Carlos A. Jiménez-Hoyos , R. Schutski , Gustavo E. Scuseria

A direct orbital optimization method is presented for density functional calculations of excited electronic states using either a real space grid or a plane wave basis set. The method is variational, provides atomic forces in the excited…

Computational Physics · Physics 2022-11-09 Aleksei V. Ivanov , Gianluca Levi , Elvar Ö. Jónsson , Hannes Jónsson

We present a theoretical investigation of resonant charge transfer in low-energy Li$^+$ ions backscattered from a MoS$_2$ surface, focusing on the influence of excited projectile states. Using a time-dependent Anderson model in the…

Strongly Correlated Electrons · Physics 2026-04-14 Thomas A. Balsamo , Faustino G. Ibarlucea , Marcelo A. Romero

Charge-transfer excited states are highly relevant for applications in molecular electronics. However, the accurate calculation of these states in large systems is challenging since wave function methods are prohibitively expensive,…

Chemical Physics · Physics 2025-05-20 Nicola Bogo , Zeyi Zhang , Martin Head-Gordon , Christopher J. Stein