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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…

Chemical Physics · Physics 2022-09-05 Rebecca Hanscam , Eric Neuscamman

The development of variational density functional theory approaches to excited electronic states is impeded by limitations of the commonly used self-consistent field (SCF) procedure. A method based on a direct optimization approach as well…

Chemical Physics · Physics 2022-11-09 Gianluca Levi , Aleksei V. Ivanov , Hannes Jónsson

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…

Chemical Physics · Physics 2026-04-02 Yorick L. A. Schmerwitz , Elli Selenius , Gianluca Levi

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…

Strongly Correlated Electrons · Physics 2019-06-19 Sergio D. Pineda Flores , Eric Neuscamman

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 demonstrate that, rather than resorting to high-cost dynamic correlation methods, qualitative failures in excited-state potential energy surface predictions can often be remedied at no additional cost by ensuring that optimal molecular…

Chemical Physics · Physics 2020-06-18 Lan Nguyen Tran , Eric Neuscamman

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

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…

Chemical Physics · Physics 2023-07-19 Antoine Marie , Hugh G. A. Burton

Orbital-optimized density functional theory (DFT) has emerged as an alternative to time-dependent (TD) DFT capable of describing difficult excited states with significant electron density redistribution, such as charge-transfer, Rydberg,…

Chemical Physics · Physics 2025-01-22 Hanh D. M. Pham , Rustam Z. Khaliullin

A novel, exact, theoretical method for the study of the excited states of a system is presented. It is demonstrated how to transform the excited state problem of one Hamiltonian into the ground state problem of an auxiliary one. From this,…

Quantum Physics · Physics 2012-06-22 Ramón Alain Miranda Quintana

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

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

Emissive organic radicals are currently of great interest for their potential use in the next generation of highly efficient organic light emitting diode (OLED) devices and as molecular qubits. However, simulating their optoelectronic…

It is proven that the exact excited-state wave function and energy may be obtained by minimizing the energy expectation value of trial wave functions that are constrained only to have the correct nodes of the state of interest. This…

Quantum Physics · Physics 2018-08-24 Federico Zahariev , Mark S. Gordon , Mel Levy

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

Elucidation of the mechanism for optical spin initialization of point defects in solids in the context of quantum applications requires an accurate description of the excited electronic states involved. While variational density functional…

Materials Science · Physics 2023-07-14 Aleksei V. Ivanov , Yorick L. A. Schmerwitz , Gianluca Levi , Hannes Jónsson

The performance of time-independent, orbital optimized calculations of excited states is assessed with respect to charge transfer excitations in organic molecules in comparison to the linear-response time-dependent density functional theory…

Chemical Physics · Physics 2024-05-22 Elli Selenius , Alec Elías Sigurdarson , Yorick L. A. Schmerwitz , Gianluca Levi

Excited electronic states of molecules and solids play a fundamental role in fields such as catalysis and electronics. In electronic structure calculations, excited states typically correspond to saddle points on the surface described by…

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…

Chemical Physics · Physics 2020-03-11 Diptarka Hait , Martin Head-Gordon

In this work, we revisited the idea of using the coupled-cluster ground state formalism to target excited states. Our main focus was targeting doubly excited states and double core hole states. Typical equation-of-motion (EOM) approaches…

Chemical Physics · Physics 2019-12-04 Joonho Lee , David W. Small , Martin Head-Gordon
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