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Rydberg excited states of molecules pose a challenge for electronic structure calculations because of their highly diffuse electron distribution. Even large and elaborate atomic basis sets tend to underrepresent the long-range tail, overly…

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…

量子物理 · 物理学 2025-10-16 Guorui Zhu , Joel Bierman , Jianfeng Lu , Yingzhou Li

We present a method for finding individual excited states' energy stationary points in complete active space self-consistent field theory that is compatible with standard optimization methods and highly effective at overcoming difficulties…

强关联电子 · 物理学 2019-04-12 Lan Nguyen Tran , Jacqueline A. R. Shea , Eric Neuscamman

Variational optimization of orbitals in time-independent density functional calculations of excited electronic states presents a significant challenge, as excited states typically correspond to saddle points on the electronic energy…

化学物理 · 物理学 2026-04-02 Yorick L. A. Schmerwitz , Elli Selenius , Gianluca Levi

We employ a generalized variational principle to improve the stability, reliability, and precision of fully excited-state-specific complete active space self-consistent field theory. Compared to previous approaches that similarly seek to…

化学物理 · 物理学 2022-09-05 Rebecca Hanscam , Eric Neuscamman

We combine recent advances in excited state variational principles, fast multi-Slater Jastrow methods, and selective configuration interaction to create multi-Slater Jastrow wave function approximations that are optimized for individual…

强关联电子 · 物理学 2019-06-19 Sergio D. Pineda Flores , Eric Neuscamman

The quantum phase estimation algorithm stands as the primary method for determining the ground state energy of a molecular electronic Hamiltonian on a quantum computer. In this context, the ability to initialize a classically tractable…

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…

化学物理 · 物理学 2023-02-15 Yorick L. A. Schmerwitz , Gianluca Levi , Hannes Jónsson

We propose a state-averaged orbital optimization scheme for improving the accuracy of excited states of the electronic structure Hamiltonian for use on near-term quantum computers. Instead of parameterizing the orbital rotation operator in…

化学物理 · 物理学 2024-04-09 Joel Bierman , Yingzhou Li , Jianfeng Lu

We present a general approach to converge excited state solutions to any quantum chemistry orbital optimization process, without the risk of variational collapse. The resulting Square Gradient Minimization (SGM) approach only requires…

化学物理 · 物理学 2020-03-11 Diptarka Hait , Martin Head-Gordon

State-specific electronic structure theory provides a route towards balanced excited-state wave functions by exploiting higher-energy stationary points of the electronic energy. Multiconfigurational wave function approximations can describe…

化学物理 · 物理学 2023-07-19 Antoine Marie , Hugh G. A. Burton

An effective optimization strategy has been developed to construct highly accurate bound state wave functions in various three-body systems. Our procedure appears to be very effective for computations of weakly bound states and various…

原子物理 · 物理学 2014-11-21 Alexei M. Frolov , David M. Wardlaw

The choice of molecular orbitals is decisive in configuration interaction calculations. In this letter, a democratic description of the ground and excited states follows an orthogonally constrained orbitals optimization to produce…

量子物理 · 物理学 2023-02-16 Saad Yalouz , Vincent Robert

Accounting for Coriolis mixing of experimentally known rotational bands with $K^{\pi}< 3^+$, non-adiabatic effects in energy and electric characteristics of excited states are investigated, within phenomenological model. The energy and wave…

核理论 · 物理学 2015-05-29 P. N. Usmanov , A. A. Okhunov , H. Abu Kassim , U. S. Salikhbaev

We propose an excited-state molecular dynamics simulation method based on variational quantum algorithms at a computational cost comparable to that of ground-state simulations. We utilize the feature that excited states can be obtained as…

化学物理 · 物理学 2023-03-02 Hirotoshi Hirai

Accurate prediction of adiabatic $0$-$0$ excited-state energies is crucial for modeling molecular photophysical processes. Here, we benchmark computational strategies for evaluating excited-state energies and singlet-triplet gaps obtained…

化学物理 · 物理学 2026-05-08 Amrita Bera , Atreyee Majumdar , Raghunathan Ramakrishnan

Adiabatic quantum computation (AQC), which is particularly useful for combinatorial optimization, becomes more powerful by using excited states, instead of ground states. However, the excited-state AQC is prone to errors due to dissipation.…

量子物理 · 物理学 2020-12-22 Hayato Goto , Taro Kanao

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…

化学物理 · 物理学 2023-11-27 Harrison Tuckman , Eric Neuscamman

This paper describes a method to do ab initio molecular dynamics in electronically excited systems within the random phase approximation (RPA). Using a dynamical variational treatment of the RPA frequency, which corresponds to the…

凝聚态物理 · 物理学 2009-10-31 Eric R. Bittner , D. S. Kosov

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…

计算物理 · 物理学 2022-11-09 Aleksei V. Ivanov , Gianluca Levi , Elvar Ö. Jónsson , Hannes Jónsson
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