Ejecting Electrons from Molecular Anions via Shine, Shake/Rattle, and Roll

Area of Science:

• Atomic and Molecular Physics
• Chemical Physics
• Spectroscopy

Background:

• Anions provide insights into electronic structure through electron detachment.
• Photoelectron and photodetachment spectroscopy are key tools for studying anions.
• Electron detachment can be induced by photons, vibrations, or rotations.

Purpose of the Study:

• To elucidate the distinct mechanisms of electron detachment from anions: "shine," "shake/rattle," and "roll."
• To discuss the selection rules governing electron ejection angular distributions for each mechanism.
• To explore the utility of these selection rules in probing anion electronic structure.

Main Methods:

• Analysis of electric-dipole transitions for "shine" detachment.
• Investigation of vibration-to-electronic nonadiabatic transitions for "shake/rattle" detachment.
• Examination of rotation-to-electronic energy transfer for "roll" detachment.

Main Results:

• Different electron detachment mechanisms exhibit unique selection rules for electron angular distribution.
• "Shine" detachment involves direct photoexcitation, while "shake/rattle" and "roll" involve vibrational and rotational energy transfer, respectively.
• Low binding energy orbitals show unique electron ejection effects due to their large radial extent.

Conclusions:

• The selection rules for electron detachment are crucial for interpreting spectroscopic data of anions.
• Understanding these mechanisms and their associated rules enhances the analysis of electronic structure.
• Novel effects are observed for electron ejection from highly diffuse, low binding energy orbitals.