Physical Chemistry

On the Role of the Electron-Dipole Interaction in Photodetachment Angular Distributions

Authors

Abstract

The importance of including long-range electron-molecule interactions in treatments of photodetachment/photoionization is demonstrated. A combined experimental and computational study of CN− detachment is presented in which near threshold anisotropy parameters (β) are measured via photoelectron imaging. Calculated β values, based on an EOM-IP-CCSD/aug-cc-pVTZ Dyson orbital, are obtained using free particle and point dipole models. The results demonstrate the influence of the molecular dipole moment in the detachment process, and provide an explanation of the near threshold behavior of the overall photodetachment cross section in CN− detachment [J. Chem. Phys. 2020, 153, 184309]

Content

Thumbnail image of Manuscript.pdf

Supplementary material

Thumbnail image of Supporting Information I ChemRxiv.pdf
Data, Data Collection and Analysis
Details of experimental procedures, data analysis and key experimental data (experimentally determined anisotropy parameters for CN- detachment) are given in this supporting information
Thumbnail image of Supporting Information II ChemRxiv.pdf
Deriving the Point Dipole Functions
This supporting information outlines the derivation of the point dipole functions (solutions of the point dipole Schrodinger equation) upon which the treatment of the photoelectron continuum is treated in the article.
Thumbnail image of Supporting Information III ChemRxiv.pdf
Photoelectron Matrix elements in the Point Dipole Approximation
Supporting information showing how the point dipole functions are used in the calculation of the photoelectron matrix elements, which are subsequently used to calculate anisotropy parameters from the Dyson orbital associated with a transition.
Thumbnail image of Supporting Information IV ChemRxiv.pdf
Overall Detachment Cross Section in the Point Dipole Approximation
This section outlines how the point dipole model can be used to calculate the overall photodetachment cross section for the ground to ground electronic band in CN- detachment. The effect of temperature is included through incorporation of the rotational populations.