TY  - JOUR
A1  - Xiong, Tao
A1  - Włodarczyk, Radosław Stanisław
A1  - Gallandi, Lukas
A1  - Körzdörfer, Thomas
A1  - Saalfrank, Peter
T1  - Vibrationally resolved photoelectron spectra of lower diamondoids
BT  - a time-dependent approach
JF  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistry
N2  - 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)].
Y1  - 2018
U6  - https://doi.org/10.1063/1.5012131
SN  - 0021-9606
SN  - 1089-7690
VL  - 148
IS  - 4
PB  - American Institute of Physics
CY  - Melville
ER  -