Vibrationally resolved photoelectron spectra of lower diamondoids
- Vibrationally resolved lowest-energy bands of the photoelectron spectra (PES) of adamantane, diamantane, and urotropine were simulated by a time-dependent correlation function approach within the harmonic approximation. Geometries and normal modes for neutral and cationic molecules were obtained from B3LYP hybrid density functional theory (DFT). It is shown that the simulated spectra reproduce the experimentally observed vibrational finestructure (or its absence) quite well. Origins of the finestructure are discussed and related to recurrences of autocorrelation functions and dominant vibrations. Remaining quantitative and qualitative errors of the DFT-derived PES spectra refer to (i) an overall redshift by ∼0.5 eV and (ii) the absence of satellites in the high-energy region of the spectra. The former error is shown to be due to the neglect of many-body corrections to ordinary Kohn-Sham methods, while the latter has been argued to be due to electron-nuclear couplings beyond the Born-Oppenheimer approximation [Gali et al., Nat. Commun.Vibrationally resolved lowest-energy bands of the photoelectron spectra (PES) of adamantane, diamantane, and urotropine were simulated by a time-dependent correlation function approach within the harmonic approximation. Geometries and normal modes for neutral and cationic molecules were obtained from B3LYP hybrid density functional theory (DFT). It is shown that the simulated spectra reproduce the experimentally observed vibrational finestructure (or its absence) quite well. Origins of the finestructure are discussed and related to recurrences of autocorrelation functions and dominant vibrations. Remaining quantitative and qualitative errors of the DFT-derived PES spectra refer to (i) an overall redshift by ∼0.5 eV and (ii) the absence of satellites in the high-energy region of the spectra. The former error is shown to be due to the neglect of many-body corrections to ordinary Kohn-Sham methods, while the latter has been argued to be due to electron-nuclear couplings beyond the Born-Oppenheimer approximation [Gali et al., Nat. Commun. 7, 11327 (2016)].…
Author details: | Tao XiongORCiDGND, Radosław Stanisław WłodarczykGND, Lukas Gallandi, Thomas KörzdörferORCiD, Peter SaalfrankORCiDGND |
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DOI: | https://doi.org/10.1063/1.5012131 |
ISSN: | 0021-9606 |
ISSN: | 1089-7690 |
Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/29390801 |
Title of parent work (English): | The journal of chemical physics : bridges a gap between journals of physics and journals of chemistry |
Subtitle (English): | a time-dependent approach |
Publisher: | American Institute of Physics |
Place of publishing: | Melville |
Publication type: | Article |
Language: | English |
Date of first publication: | 2018/01/29 |
Publication year: | 2018 |
Release date: | 2022/02/09 |
Volume: | 148 |
Issue: | 4 |
Number of pages: | 9 |
Funding institution: | DFG-Forschergruppe 1282 [Sa 547/11-1]; Cluster of Excellence 314 "Unifying Concepts in Catalysis"; Deutsche Forschungsgemeinschaft (DFG)German Research Foundation (DFG) [KO 4876/4-1] |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
DDC classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
Peer review: | Referiert |