Vibronic coupling effects in resonant auger spectra of H2O

• Verfasst von: Eroms, Matthis [VerfasserIn]
• Verfasst von: Jungen, Martin [VerfasserIn]
• Verfasst von: Meyer, Hans-Dieter [VerfasserIn]
• Titel: Vibronic coupling effects in resonant auger spectra of H2O
• Verf.angabe: Matthis Eroms, Martin Jungen and Hans-Dieter Meyer
• E-Jahr: 2012
• Jahr: 26 November 2012
• Umfang: 11 S.
• Fussnoten: Im Titel ist in der chemischen Formel für Wasser (H2O) die "2" tief gestellt ; Gesehen am 22.11.2018
• Titel Quelle: Enthalten in: The journal of physical chemistry <Washington, DC> / A
• Ort Quelle: Washington, DC : Soc., 1997
• Jahr Quelle: 2012
• Band/Heft Quelle: 116(2012), 46, Seite 11140-11150
• ISSN Quelle: 1520-5215
• DOI: doi:10.1021/jp304666k
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1583971971

Abstract

We present a theoretical investigation of the resonant Auger effect in gas-phase water. As in our earlier work, the simulation of nuclear dynamics is treated in a one-step picture, because excitation and decay events cannot be disentangled. Extending this framework, we now account for the vibronic coupling in the cationic final states arising from degeneracies in their potential energy surfaces (PESs). A diabatization of the cationic states permits a correct treatment of non Born-Oppenheimer dynamics leading to a significantly better agreement with experimental results. Moreover, we arrive at a more balanced understanding of the various spectral features that can be attributed to nuclear motion in the core-excited state or to vibronic coupling effects. The nuclear equations of motion have been solved using the multiconfiguration time-dependent Hartree (MCTDH) method. The cationic PESs were recalculated using the coupled electron pair approach (CEPA) whereas previously a multireference configuration interaction method had been employed.