AI Article Synopsis
- The study examines how the conformational population affects photoelectron circular dichroism (PECD) spectroscopy, which has provided deep insights into molecular processes and geometries.
- The research highlights the significant role of methyl group rotations in influencing the PECD signal, linking theoretical predictions with experimental observations.
- Using norcamphor as a benchmark, the work achieves strong alignment between experimental results and theory, enhancing understanding of how molecular rotations impact PECD, particularly in comparison to camphor.
Article Abstract
In this work we address a specific experimental and theoretical question regarding the influence of a conformational population in the modeling of photoelectron circular dichroism (PECD) spectroscopy. In the past two decades, PECD has revealed a rich and complex phenomenology in molecular processes with unprecedented insight, especially in molecular geometry sensitivity. Since the early development of this spectroscopy, theory has pointed out the importance of conformer influence on PECD; in particular, the rotation of methyl groups was surprisingly found to be responsible for strong modulation of the PECD signal. Here, to advance understanding of the effect of rotations, we have chosen to study norcamphor, a single-conformer molecule, as a benchmark for a PECD comparison between experiment and theory at the density functional theory (DFT) and time-dependent density functional theory (TDDFT) levels. The excellent agreement between experimental data and theory for norcamphor sheds light on the influence of rotations and gives a solid explanation for the reasonable qualitative agreement in the PECD of camphor, where three methyl groups are added to the same molecular structure.
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