Conical intersections in electron photodetachment spectroscopy : theory and applications

Contents: Electron spectroscopies Scope of this work Vibronic Coupling Model Vibronic wave functions The initial state The final state: Nonadiabatic Ansatz Time-independent nonrelativistic wave functions Wave functions including the spin-orbit interaction Determination of time-independent wave functions Nonrelativistic Schr\uf6dinger equation Schr\uf6dinger equation including the spin-orbit interaction Spectral intensity distribution function Nonrelativistic formulation Inclusion of spin-orbit coupling Hamiltonians Coulomb or nonrelativistic diabatic Hamiltonian, Hd Kinetic energy operator Computational issues Construction of diabatic Hamiltonians for bound states Optimal bases and Franck\u2013Condon overlaps Lanczos procedure: Open-ended fine grained parallel approach Applications Overview: Conical intersections not required by symmetry Azolyls: Electronic structure Imidazolyl Pyrazolyl Pyrrolyl Pyrrolyl: Detailed computations Electronic structure treatment Construction and accuracy of Hd Nascent Hd Improving the accuracy and extending the domain of utility of Hd Sensitivity of simulated photoelectron spectrum to Hd, w Photoelectron spectrum of pyrrolyl Isopropoxy Electronic structure treatment An unexpected conical topography Photoelectron spectrum of isopropoxide ImplicationsPeer reviewed: YesNRC publication: Ye