Prediction challenge: First principles simulation of the ultrafast electron diffraction spectrum of cyclobutanone

TL;DR

This study uses advanced ab initio simulations to predict ultrafast electron diffraction spectra of cyclobutanone, aiming to validate theoretical models against upcoming experimental data and identify key spectral features.

Contribution

It demonstrates the first principles prediction of ultrafast electron diffraction signals for cyclobutanone, integrating quantum-classical simulations with experimental planning.

Findings

Identification of dissociation channels C3 and C2 post-excitation.

Simulation of spectral features distinguishing ring-opened intermediates.

Analysis of predicted spectral accuracy and potential errors.

Abstract

Computer simulation has long been an essential partner of ultrafast experiments, allowing the assignment of microscopic mechanistic detail to low-dimensional spectroscopic data. However, the ability of theory to make a priori predictions of ultrafast experimental results is relatively untested. Herein, as a part of a community challenge, we attempt to predict the signal of an upcoming ultrafast photochemical experiment using state-of-the-art theory in the context of preexisting experimental data. Specifically, we employ ab initio Ehrenfest with collapse to a block (TAB) mixed quantum-classic simulations to describe the real-time evolution of the electrons and nuclei of cyclobutanone following excitation to the 3s Rydberg state. The gas-phase ultrafast electron diffraction (GUED) signal is simulated for direct comparison to an upcoming experiment at the Stanford Linear Accelerator Laboratory. Following initial ring-opening, dissociation via two distinct channels is observed: the C3 dissociation channel, producing cyclopropane and CO, and the C2 channel, producing CH$_2$CO and C$_2$H$_4$. Direct calculations of the GUED signal indicate how the ring-opened intermediate, the C2 products, and the C3 products can be discriminated in the GUED signal. We also report an a priori analysis of anticipated errors in our predictions: without knowledge of the experimental result, which features of the spectrum do we feel confident we have predicted correctly, and which might we have wrong?