Rate equations for nitrogen molecules in ultrashort and intense x-ray pulses

TL;DR

This paper develops quantum rate equations to model nitrogen molecule ionization and dissociation under intense ultrashort x-ray pulses, successfully matching experimental ion yields and revealing pulse duration effects on molecular fragmentation.

Contribution

It introduces a detailed molecular rate-equation model for N₂ under ultrafast x-ray irradiation, extending previous phenomenological approaches.

Findings

Effective pulse energy decreases with shorter pulses.

Ion yields and average charge states agree well with experiments.

Shorter pulses alter fragmentation patterns and reduce absorption.

Abstract

We study theoretically the quantum dynamics of nitrogen molecules (N$_2$) exposed to intense and ultrafast x-rays at a wavelength of 1.1 nm (1100 eV photon energy) from the Linac Coherent Light Source (LCLS) free electron laser. Molecular rate equations are derived to describe the intertwined photoionization, decay, and dissociation processes occurring for N$_2$. This model complements our earlier phenomenological approaches, the single-atom, symmetric-sharing, and fragmentation-matrix models of J. Chem. Phys. $\mathbf{136}$, 214310 (2012). Our rate-equations are used to obtain the effective pulse energy at the sample and the time scale for the dissociation of the metastable dication N$_2^{2+}$. This leads to a very good agreement between the theoretically and experimentally obtained ion yields and, consequently, the average charge states. The effective pulse energy is found to decrease with shortening pulse duration. This variation together with a change in the molecular fragmentation pattern and frustrated absorption---an effect that reduces absorption of x-rays due to (double) core hole formation---are the causes for the drop of the average charge state with shortening LCLS pulse duration discovered previously.