Title

Intruder Peak-Free Transient Inner-Shell Spectra Using Real-Time Simulations

Document Type

Article

Publication Date

2-8-2022

Abstract

Real-time methods are convenient for simulating core-level absorption spectra but suffer from nonphysical intruder peaks when using atom-centered basis sets. In transient absorption spectra, these peaks exhibit highly nonphysical time-dependent modulations in their energies and oscillator strengths. In this paper, we address the origins of these intruder peaks and propose a straightforward and effective solution based on a filtered dipole operator. In combination with real-time time-dependent density functional theory (RT-TDDFT), we demonstrate how to compute intruder-free attosecond transient X-ray absorption spectra for the aminophenol (CHNO) oxygen and nitrogen K-edges and the α-quartz (SiO) silicon L-edge. Without filtering, the computed spectra are qualitatively wrong. This procedure is suitable for both static and transient inner-shell spectroscopy studies and can easily be implemented in a range of real-time methodologies.

Publication Source (Journal or Book title)

Journal of chemical theory and computation

First Page

992

Last Page

1002

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