Selected Configuration Interaction for Resonances
arXiv:2407.08576 · doi:10.1021/acs.jpclett.4c02060
Abstract
Electronic resonances are metastable states that can decay by electron loss. They are ubiquitous across various fields of science, such as chemistry, physics, and biology. However, current theoretical and computational models for resonances cannot yet rival the level of accuracy achieved by bound-state methodologies. Here, we generalize selected configuration interaction (SCI) to treat resonances using the complex absorbing potential (CAP) technique. By modifying the selection procedure and the extrapolation protocol of standard SCI, the resulting CAP-SCI method yields resonance positions and widths of full configuration interaction quality. Initial results for the shape resonances of \ce{N2-} and \ce{CO-} reveal the important effect of high-order correlation, which shifts the values obtained with CAP-augmented equation-of-motion coupled-cluster with singles and doubles by more than \SI{0.1}{\eV}. The present CAP-SCI approach represents a cornerstone in the development of highly-accurate methodologies for resonances.
10 pages, 2 figures (supporting information available)
References in corpus (26)
- Heat-bath Configuration Interaction: An efficient selected CI algorithm inspired by heat-bath sampling
- Semistochastic Heat-bath Configuration Interaction method: selected configuration interaction with semistochastic perturbation theory
- A Mountaineering Strategy to Excited States: Highly-Accurate Reference Energies and Benchmarks
- A deterministic alternative to the full configuration interaction quantum Monte Carlo method
- An adaptive configuration interaction approach for strongly correlated electrons with tunable accuracy
- Modern Approaches to Exact Diagonalization and Selected Configuration Interaction with the Adaptive Sampling CI Method
- The Quest For Highly Accurate Excitation Energies: A Computational Perspective
- Quantum Package 2.0: An Open-Source Determinant-Driven Suite of Programs
- CASSCF with Extremely Large Active Spaces using the Adaptive Sampling Configuration Interaction Method
- QUESTDB: a database of highly-accurate excitation energies for the electronic structure community
- The Ground State Electronic Energy of Benzene
- Excited states using semistochastic heat-bath configuration interaction
- Hybrid stochastic-deterministic calculation of the second-order perturbative contribution of multireference perturbation theory
- Excited States of Methylene, Polyenes, and Ozone from Heat-Bath Configuration Interaction
- Selected configuration interaction dressed by perturbation
- Machine Learning Configuration Interaction
- Fixed-Node Diffusion Monte Carlo potential energy curve of the fluorine molecule F2 using selected configuration interaction trial wavefunctions
- The Shape of Full Configuration Interaction to Come
- Almost exact energies for the Gaussian-2 set with the semistochastic heat-bath configuration interaction method
- Orbital Optimization in Selected Configuration Interaction Methods
- The performance of CIPSI on the ground state electronic energy of benzene
- Accurate full configuration interaction correlation energy estimates for five- and six-membered rings
- Non-iterative triples excitations in equation-of-motion coupled-cluster theory for electron attachment with applications to bound and temporary anions
- Ground- and Excited-State Dipole Moments and Oscillator Strengths of Full Configuration Interaction Quality
- Spin-adapted selected configuration interaction in a determinant basis
- Rationale for the Extrapolation Procedure in Selected Configuration Interaction