Related Experiment Video
Updated: Jun 19, 2026

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−
Published on: July 27, 2018
The photoelectron spectrum of the ethoxide anion: conical intersections, the spin-orbit interaction, and sequence
Joseph J Dillon1, David R Yarkony
1Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
Abstract:
The negative ion photoelectron spectrum of the ethoxide anion (ethoxide-h(5)) and that of its fully deuterated analog, ethoxide-d(5), are calculated using the multimode vibronic coupling approach. A two state quasidiabatic Hamiltonian H(d) is constructed which includes all terms through second order in the full 18 dimensional internal coordinate space. H(d) is centered at the ab initio determined minimum energy crossing (MEX) point on the symmetry-allowed (2)A(")-(2)A(') accidental seam of conical intersection and determined from ab initio energy gradients and derivative couplings. It reproduces the local topography of the (2)A(")-(2)A(') MEX, in addition to accurately representing the geometries, energetics, and harmonic frequencies of equilibrium and saddle point structures located on the ground electronic state potential energy surface in the vicinity of the MEX. Spin-orbit effects are included. The results for ethoxy-h(5) are compared to photoelectron and slow electron velocity-map imaging (SEVI) spectra. By comparing the measured and predicted photoelectron spectrum, the accuracy of the electronic structure treatment is inferred. The existence of sequence bands in the SEVI spectrum is established.
More Related Videos
08:23Analyzing the Photo-oxidation of 2-propanol at Indoor Air Level Concentrations Using Field Asymmetric Ion Mobility Spectrometry
Published on: June 14, 2018
08:04Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Related Concept Videos
UV–Vis Spectroscopy: Molecular Electronic Transitions
Electron Paramagnetic Resonance (EPR) Spectroscopy: Organic Radicals
Electron Configurations
The relative energies of the subshells determine the order in which atomic orbitals are filled (1s, 2s, 2p, 3s, 3p, 4s,...
Molecular Orbital Theory II
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
IR and UV–Vis Spectroscopy of Aldehydes and Ketones