Work

A relativistic third-order algebraic diagrammatic construction theory for electron detachment, attachment, and excitation problems

Year: 2025

Type: article

Abstract: We present the theory and implementation of a relativistic third-order algebraic diagrammatic construction [ADC(3)] method based on a four-component (4c) Dirac-Coulomb Hamiltonian for the calculation of ionization potentials (IPs), electron affinities (EAs), and excitation energies (EEs). Benchmarking calculations for IP, EA, and EE were performed on both atomic and molecular systems to assess the accuracy of the newly developed four-component relativistic ADC(3) method. The results show good agreement with the available experimental data. The Hermitian nature of the 4c-ADC(3) Hamiltonian, combined with the perturbative truncation of the wave function, offers significant computational advantages over the standard equation-of-motion coupled-cluster approach, particularly for property calculations. The method's suitability for property calculations is further demonstrated by computing oscillator strengths and excited-state dipole moments for heavy elements.

Source: The Journal of Chemical Physics

DOI: 10.1063/5.0246920

Authors: Sudipta Chakraborty, Tamoghna Mukhopadhyay, Malaya K. Nayak, Achintya Kumar Dutta

Institutions: Indian Institute of Technology Bombay, Bhabha Atomic Research Centre, Homi Bhabha National Institute

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