Work

Complex-Variable Equation-of-Motion Coupled-Cluster Singles and Doubles Theory with the Resolution-of-the-Identity Approximation

Year: 2025

Type: article

Abstract: We present an implementation of complex-variable equation-of-motion coupled- cluster singles and doubles (EOM-CCSD) theory with the resolution-of-the-identity (RI) approximation. Complex-variable methods are used in the framework of non- Hermitian quantum chemistry to treat electronic resonances. As test cases, we study differenttypesofresonancesofN2 andCO, namelytemporaryanions, Starkresonances, autoionizing Rydberg states and core-ionized states that decay by the Auger-Meitner effect. Temporary anions are treated with the complex basis function (CBF) method and different variants of the complex absorbing potential (CAP) method. The other resonances are only treated with CBFs. The memory requirements of our implementa- tion are significantly lower than those of canonical EOM-CCSD. We demonstrate that the RI error is smaller than the basis set error for all types of resonances. However, when the size of the decay width approaches the magnitude of the RI error, the width is predicted qualitatively wrong with the RI approximation. In addition, when an ad- equate auxiliary basis set is not available, i.e., for autoionizing Rydberg states and for core-ionized states, the RI error in the total decay width increases by a factor 10.

Source: The Journal of Physical Chemistry A

DOI: 10.1021/acs.jpca.5c01313

Authors: Simen Camps, Cansu Utku, Joel Creutzberg, Thomas-C. Jagau

Institution: KU Leuven

Language: English

Topic: Advanced Chemical Physics Studies

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: green