Aufbau suppressed coupled cluster as a post-linear-response method

2025/06/20 by Trine Kay Quady, Quady, Trine Kay, Harrison Tuckman +3 · 1 voice · 2 citations
Chemistry · Engineering · Physics and Astronomy · #Advanced Chemical Physics Studies #Charge (physics) #Chemical Physics (physics.chem-ph) #Cluster (spacecraft) #Coupled cluster #Excited state #FOS: Physical sciences #Initialization #Nonlinear Optical Materials Studies #Order (exchange) #Spectroscopy and Quantum Chemical Studies

paper · pdf · doi:10.48550/arxiv.2506.16680

published in arXiv (Cornell University) (Cornell University)

openalex publication_date 2025/06/20 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

We investigate the ability of Aufbau suppressed coupled cluster theory to act as a post-linear-response correction to widely used linear response methods for electronically excited states. We find that the theory is highly resilient to shortcomings in the underlying linear response method, with final results from less accurate starting points nearly as good as those from the best starting points. This pattern is especially stark in charge transfer states, where the approach converts starting points with multi-eV errors into post-linear-response results with errors on the order of 0.1 eV. These findings highlight the ability of Aufbau suppressed coupled cluster to perform its own orbital relaxations and raise the question of whether initializing it with an orbital relaxed reference is worth the trouble.

Citations

• The Approximation of One Matrix by Another of Lower Rank
• Equation-of-Motion Coupled-Cluster Methods for Open-Shell and Electronically Excited Species: The Hitchhiker's Guide to Fock Space
• Progress in Time-Dependent Density-Functional Theory
• Recent developments in the PySCF program package
• Fast and Accurate Charge Transfer Excitations via Nested Aufbau Suppressed Coupled Cluster
• Improving Aufbau Suppressed Coupled Cluster Through Perturbative Analysis
• Exploring Ligand-to-Metal Charge-transfer States in the Photo-Ferrioxalate System using Excited-State Specific Optimization
• Spin Coupling Effect on Geometry-Dependent X-ray Absorption of Diradicals
• Double excitation energies from quantum Monte Carlo using state-specific energy optimization
• Optimization stability in excited state-specific variational Monte Carlo
• Energy Landscape of State-Specific Electronic Structure Theory
• A Promising Intersection of Excited-State-Specific Methods from Quantum Chemistry and Quantum Monte Carlo
• Applying generalized variational principles to excited-state-specific complete active space self-consistent field theory
• Improving excited state potential energy surfaces via optimal orbital shapes
• A generalized variational principle with applications to excited state mean field theory
• Tracking excited states in wave function optimization using density matrices and variational principles
• Size consistent excited states via algorithmic transformations between variational principles
• An efficient variational principle for the direct optimization of excited states
• Time-dependent density functional theory: Past, present, and future
• Stability conditions and nuclear rotations in the Hartree-Fock theory

Cited by

• One-Body Properties and Their Perturbative Accuracy with Aufbau Suppressed Coupled Cluster Theory
• Unphysical Solutions in Coupled-Cluster-Based Random Phase Approximation and How to Avoid Them

Discussions

• Check out this recent paper from researchers at UC Berkeley, who use Q-Chem's EOM-CC, TDDFT, and excited state analysis module to investigate a new correction to linear response methods for excited st [bsky, 0 points, 0 comments]

Related

• Improving Aufbau Suppressed Coupled Cluster Through Perturbative Analysis
• Fast and Accurate Charge Transfer Excitations via Nested Aufbau Suppressed Coupled Cluster
• One-Body Properties and Their Perturbative Accuracy with Aufbau Suppressed Coupled Cluster Theory
• A reduced cost equation of motion coupled cluster method for excited states based on state-specific natural orbitals: Theory, Implementation, Benchmark
• Accelerated basis-set convergence of coupled-cluster excitation energies using the density-based basis-set correction method