Year: 2024
Type: article
Abstract: The quantum equation-of-motion (qEOM) method with single and double excitations (qEOM-SD) has been proposed to study electronically excited states, but it fails to handle states dominated by double excitations. In this work, we reformulate the qEOM method within the effective Hamiltonian framework that satisfies the killer condition, and then present an efficient implementation incorporating single, double, and triple excitations. To reduce computational complexity, we employ point-group symmetry and perturbation theory to screen triple excitations, effectively reducing the scaling from N o 6 N v 6 to N o 5 N v 5, where N o and N v are the numbers of occupied and virtual spin orbitals, respectively. Furthermore, we account for the effect of neglected triple excitations by introducing a perturbative correction to the excitation energy. We apply this method to challenging cases where the qEOM-SD method exhibits significant errors, such as the 2 1 Δ state of CH + and the 2 1 Σ state of HF. Our new method achieves energy errors below 0.18 eV while incorporating less than 8.2% of triple excitations. Additionally, we extend the operator screening technique to the quantum subspace expansion method for the efficient inclusion of selected triple excitations.
Institution: University of Science and Technology of China
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: green
Awards: G1309649911, G4681129812, G4842921585
OpenAlex ID: W4403186447