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Density functional calculations of Rydberg excited states up to high energy are carried out for several molecules using an approach where the orbitals are variationally optimized by converging on saddle points on the electronic energy…

Calculations of the lowest valence {\pi}* as well as the 3s and higher energy 3p{\sigma} Rydberg excited states of the CO2 molecule are carried out using density functionals with variational optimization of the orbitals, an approach…

化学物理 · 物理学 2026-04-08 Darío Barreiro-Lage , Gianluca Levi , Hannes Jonssón , Thanja Lamberts

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…

化学物理 · 物理学 2020-06-18 Lan Nguyen Tran , Eric Neuscamman

We investigate configuration-interaction (CI) calculations on a basis of molecular orbitals generated by preliminary density-functional theory (DFT) calculations. We use this CI/DFT framework to improve the modeling of core-excited states…

化学物理 · 物理学 2025-09-11 Giorgio Visentin , Francois Mauger

Selective configuration interaction methods approximate correlated molecular ground- and excited states by considering only the most relevant Slater determinants in the expansion. While a recently proposed neural-network-assisted approach…

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

The nuclear-electronic orbital (NEO) approach incorporates nuclear quantum effects into quantum chemistry calculations by treating specified nuclei quantum mechanically, equivalently to the electrons. Within the NEO framework, excited…

化学物理 · 物理学 2025-03-19 Christopher L. Malbon , Sharon Hammes-Schiffer

Studying the complex quantum dynamics of interacting many-body systems is one of the most challenging areas in modern physics. Here, we use machine learning (ML) models to identify the symmetrized base states of interacting Rydberg atoms of…

量子物理 · 物理学 2021-08-13 Daryl Ryan Chong , Minhyuk Kim , Jaewook Ahn , Heejeong Jeong

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 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…

化学物理 · 物理学 2023-08-31 Fábris Kossoski , Pierre-François Loos

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

Trapped Rydberg ions represent a flexible platform for quantum simulation and information processing which combines a high degree of control over electronic and vibrational degrees of freedom. The possibility to individually excite ions to…

量子气体 · 物理学 2020-09-30 Filippo Maria Gambetta , Chi Zhang , Markus Hennrich , Igor Lesanovsky , Weibin Li

Assembled arrays of individual atoms with Rydberg-mediated interactions provide a powerful platform for the simulation of many-body spin Hamiltonians as well as the implementation of universal gate-based quantum information processing. We…

The Rydberg excitation blockade has been at the heart of an impressive array of recent achievements; however, state-mixing interactions can compromise its efficiency. When ultracold atoms are excited to Rydberg states near F\"orster…

原子物理 · 物理学 2022-09-05 Milo Eder , Andrew Lesak , Abigail Plone , Tomohisa Yoda , Michael Highman , Aaron Reinhard

We test a set of multiconfigurational wavefunction approaches for calculating the ground state electron population for a two-site Anderson model representing a molecule on a metal surface. In particular, we compare (i) a Hartree Fock like…

化学物理 · 物理学 2022-07-19 Junhan Chen , Wenjie Dou , Joseph Subotnik

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

We theoretically investigate trapped ions interacting with atoms that are coupled to Rydberg states. The strong polarizabilities of the Rydberg levels increases the interaction strength between atoms and ions by many orders of magnitude, as…

量子物理 · 物理学 2016-07-27 Thomas Secker , Rene Gerritsma , Alexander W. Glaetzle , Antonio Negretti

Quantum information processing with neutral atoms relies on Rydberg excitation for entanglement generation. While the use of heavy divalent or open-shell elements, such as strontium or ytterbium, has benefits due to their optically active…

We present an efficient method for producing $N$ particle entangled states using Rydberg blockade interactions. Optical excitation of Rydberg states that interact weakly, yet have a strong coupling to a second control state is used to…

量子物理 · 物理学 2010-11-01 M. Saffman , K. Molmer

We demonstrate how to determine numerically nearly exact orthonormal orbitals that are optimal for evaluation of the energy of arbitrary (correlated) states of atoms and molecules by minimization of the energy Lagrangian. Orbitals are…

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