https://cnrs.hal.science/hal-03044679Lara-Moreno, MiguelMiguelLara-MorenoISM - Institut des Sciences Moléculaires - Université Montesquieu - Bordeaux 4 - UB - Université Sciences et Technologies - Bordeaux 1 - École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB) - INC - Institut de Chimie du CNRS - CNRS - Centre National de la Recherche ScientifiqueStoecklin, ThierryThierryStoecklinISM - Institut des Sciences Moléculaires - Université Montesquieu - Bordeaux 4 - UB - Université Sciences et Technologies - Bordeaux 1 - École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB) - INC - Institut de Chimie du CNRS - CNRS - Centre National de la Recherche ScientifiqueHalvick, PhilippePhilippeHalvickISM - Institut des Sciences Moléculaires - Université Montesquieu - Bordeaux 4 - UB - Université Sciences et Technologies - Bordeaux 1 - École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB) - INC - Institut de Chimie du CNRS - CNRS - Centre National de la Recherche ScientifiqueLoison, Jean-ChristopheJean-ChristopheLoisonSingle-center approach for photodetachment and radiative electron attachment: Comparison with other theoretical approaches and with experimental photodetachment dataHAL CCSD2019[SDU] Sciences of the Universe [physics][PHYS] Physics [physics][CHIM] Chemical SciencesStoecklin, Thierry2020-12-07 18:54:572023-02-08 17:11:152020-12-11 10:04:32enJournal articleshttps://cnrs.hal.science/hal-03044679/document10.1103/physreva.99.033412application/pdf1A single-center method for calculating photodetachment cross section for anions and radiative electron attachment cross section for neutral molecules by microreversibility is presented. It uses the integral equation method to calculate the ejected electron's continuum wave function while the single-electron bound function of the anion is described by the Dyson orbital. It is compared with related theoretical approaches and benchmarked to the experimental photodetachment cross sections of O 2 − , OH − , and CN −. The use of the plane-wave approximation of the ejected electron wave function combined with the Hartree-Fock frozen-core approximation of the Dyson orbital is also considered and its results are compared with those of our methods and with experiment. A good agreement between the calculated photodetachment cross sections and the experimental data is obtained for O 2 − and CN − when using the three methods. For OH − , the calculated scattering-wave electron photodetachment cross sections agree well with two most recent sets of experimental data among the three available while the plane-wave results disagree with all the experimental and theoretical data. The different approaches to calculate the Dyson orbital are also discussed as well as the convergence of the calculations with respect to the choice of the one-electron basis set. The approximation of Dyson orbitals by Kohn-Sham orbitals appears to overestimate the photodetachment cross section.