K-shell Core Electron Excitations in the Electronic Stopping of Protons in Water

TL;DR

This study uses first-principles simulations to analyze how core electron excitations in water influence electronic stopping power during proton irradiation, revealing significant contributions from K-shell electrons and differences from traditional models.

Contribution

It provides the first detailed ab initio analysis of core electron effects on electronic stopping in water, highlighting their importance beyond valence electrons.

Findings

Core electron excitations contribute up to one-third of stopping power at high proton velocities.

Significant differences exist between first-principles results and perturbation models.

K-shell holes remain highly localized despite their role in energy transfer.

Abstract

Developing a detailed understanding for the role of core electron excitation in liquid water under proton irradiation has become important due to the growing use of proton beams in radiation oncology. Using a first-principles, non-equilibrium simulation approach based on real-time time-dependent density functional theory, we determine the electronic stopping power, the velocity-dependent energy transfer rate from irradiating ions to electrons. The electronic stopping power curve agrees quantitatively over the entire velocity range for which experimental data is available. Also notably, we observe significant differences between our first-principles results and commonly-used perturbation theoretic models. Excitations of the water molecules' oxygen core electrons are a crucial factor in determining the electronic stopping power curve beyond its maximum. The core electron contribution is responsible for as much as one-third of the stopping power at the high proton velocity of 8.0 a.u. (1.6 MeV). These K-shell core electron excitations not only provide an additional channel for the energy transfer but they also significantly influence the valence electron excitation. In the excitation process, generated holes remain highly localized within a few angstroms around the irradiating proton path whereas electrons are excited away from the path. In spite of its great contribution to the electronic stopping power, the K-shell electrons play a rather minor role in terms of the excitation density: Only one percent of the hole population comprises K-shell holes, even at the high proton velocity of 8.0 a.u.. The excitation behavior revealed here is distinctly different from that of X/gamma-ray photon radiation, which is the most commonly used type of ionizing radiation in radiation oncology.