Simulation of photoelectron spectra using the reflection principle in combination with unrestricted excitation ADC(2) to assess the accuracy of excited-state calculations
The gas-phase photoelectron spectra of ethene, formaldehyde, formic acid and difluoromethane are simulated using the reflection principle and the unrestricted second-order algebraic diagrammatic construction [UADC(2)] scheme of the polarization propagator for the computation of the vertical-excited...
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| Hauptverfasser: | , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
21 October 2011
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| In: |
ChemPhysChem
Year: 2011, Jahrgang: 12, Heft: 17, Pages: 3180-3191 |
| ISSN: | 1439-7641 |
| DOI: | 10.1002/cphc.201100485 |
| Online-Zugang: | Verlag, Volltext: http://dx.doi.org/10.1002/cphc.201100485 Verlag, Volltext: http://onlinelibrary.wiley.com/doi/10.1002/cphc.201100485/abstract 
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| Verfasserangaben: | Stefan Knippenberg, Pierre Eisenbrandt, Lukáš Šištík, Petr Slavíček, and Andreas Dreuw |
| Zusammenfassung: | The gas-phase photoelectron spectra of ethene, formaldehyde, formic acid and difluoromethane are simulated using the reflection principle and the unrestricted second-order algebraic diagrammatic construction [UADC(2)] scheme of the polarization propagator for the computation of the vertical-excited states of the cations at the equilibrium geometry of the parent neutral molecule. Comparison is made with experimental spectra and the established highly accurate ionization IP-ADC(3) theory to gain insight into the accuracy and applicability of recently developed excitation UADC schemes. Within UADC(2), we distinguish between the strict and extended schemes UADC(2)-s and UADC(2)-x. While the latter approach is found to slightly underestimate the experimental photoelectron spectra by 0.3 eV and can thus be regarded as a reliable scheme within the limits of the applied reflection principle and the underlying approximations, the UADC(2)-s scheme tends to overestimate the excitation energies by about 0.5 eV. Time-dependent density functional theory is also applied in combination with the standard B3LYP xc functional and turns out to be a useful computational tool for the simulation of the photoelectron spectra of the studied species. |
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| Beschreibung: | Gesehen am 14.12.2017 |
| Beschreibung: | Online Resource |
| ISSN: | 1439-7641 |
| DOI: | 10.1002/cphc.201100485 |