Excited-State Forces within a First-Principles Green’s Function Formalism

2002/07/31 by Sohrab Ismail‐Beigi, Sohrab Ismail-Beigi Steven G. Louie, Steven G. Louie · 117 citations
Chemistry · Earth and Planetary Sciences · Physics and Astronomy · #Advanced Chemical Physics Studies #Atmospheric Ozone and Climate #Atomic physics #Computation #Computer science #Excitation #Excited electronic state #Excited state #Formalism (music) #Physics #Quantum mechanics #Spectroscopy and Laser Applications #cond-mat.mtrl-sci

paper · pdf · doi:10.1103/physrevlett.90.076401

published in Physical Review Letters 90(7), 076401 (American Physical Society) · 2 figures and 2 tables

arxiv created 2002/11/19 · openalex publication_date 2003/02/19 · arxiv updated 2013/05/29 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

We present a new first-principles formalism for calculating forces for optically excited electronic states using the interacting Green's function approach with the GW Bethe-Salpeter-equation method. This advance allows for efficient computation of gradients of the excited-state Born-Oppenheimer energy, allowing for the study of relaxation, molecular dynamics, and photoluminescence of excited states. The approach is tested on photoexcited carbon dioxide and ammonia molecules, and the calculations accurately describe the excitation energies and photoinduced structural deformations.

Citations

• Electron-hole excitations and optical spectra from first principles
• Electronic excitations: density-functional versus many-body Green’s-function approaches
• Iterative minimization techniques forab initiototal-energy calculations: molecular dynamics and conjugate gradients

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