TY - JOUR
T1 - Electronic excitations in a ladder type fluoranthenopyracylene in its neutral and charged states
T2 - A theoretical and experimental study
AU - Lukeš, Vladimír
AU - Matuszná, Katarína
AU - Rapta, Peter
AU - Dunsch, Lothar
AU - Aquino, Adelia Justina Aguiar
AU - Lischka, Hans
N1 - Funding Information:
The authors would like to thank to Dr. Niels Schulte and Prof. Arnulf-Dieter Schlüter for the preparation of the compound under study and also to Prof. Harald-Friedrich Kauffmann, Dr. Franz Milota and Mgr. Jaroslaw Sper- ling for performing additional optical measurements and helpful discussion. A very special thanks goes to Prof. Shaul Mukamel for the opportunity to perform calculations using the CEO program package developed in his group and for constructive comments. This work was supported by the Austrian Science Foundation (Project P18233 and Special Research Program F16 (ADLIS)). This work was also supported by the Slovak Scientific Grant Agency (Projects No. 1/3036/06, 1/2021/05 and 1/3579/06). Financial support by the Alexander von Humboldt Foundation (AvH) for P.R. and the AvH Project 3Fokoop DEU/1063827 is also duly acknowledged. K.M. thanks to the J. von Neumann Institut for Computing for usage of the supercomputer.
PY - 2007
Y1 - 2007
N2 - This work reports on theoretical and spectroelectrochemical studies of a thermally and chemically stable fluoranthenopyracylene ladder type molecule 7,10,17,20 tetra-p-dodecylphenyl(bisfluorantheno[8,9-a,c]) pyracylene. Optimal geometries were evaluated for neutral and positively/negatively charged states performing density functional theory (DFT) calculations. Absorption spectral line frequencies as well as oscillator strengths were calculated using the time-dependent DFT and collective electronic oscillator (CEO) methods. The calculated optical spectra are in good agreement with the experimental measurements in solution. The difference of charged states produced by reduction and/or oxidation versus the electronic neutral forms on the vertical excitation energies and CEO electronic density matrix distribution has been characterized and compared to the geometrical changes of the molecular fragments. The localization of excitation in the optical transition of the charged states shows that the excitation is less separated and shows larger electronic coherence in comparison to the neutral form.
AB - This work reports on theoretical and spectroelectrochemical studies of a thermally and chemically stable fluoranthenopyracylene ladder type molecule 7,10,17,20 tetra-p-dodecylphenyl(bisfluorantheno[8,9-a,c]) pyracylene. Optimal geometries were evaluated for neutral and positively/negatively charged states performing density functional theory (DFT) calculations. Absorption spectral line frequencies as well as oscillator strengths were calculated using the time-dependent DFT and collective electronic oscillator (CEO) methods. The calculated optical spectra are in good agreement with the experimental measurements in solution. The difference of charged states produced by reduction and/or oxidation versus the electronic neutral forms on the vertical excitation energies and CEO electronic density matrix distribution has been characterized and compared to the geometrical changes of the molecular fragments. The localization of excitation in the optical transition of the charged states shows that the excitation is less separated and shows larger electronic coherence in comparison to the neutral form.
KW - Coherence
KW - Delocalization
KW - Optical spectra
KW - TDDFT
KW - π-conjugated system
UR - http://www.scopus.com/inward/record.url?scp=34547235507&partnerID=8YFLogxK
U2 - 10.1524/zpch.2007.221.7.911
DO - 10.1524/zpch.2007.221.7.911
M3 - Article
AN - SCOPUS:34547235507
SN - 0942-9352
VL - 221
SP - 911
EP - 928
JO - Zeitschrift fur Physikalische Chemie
JF - Zeitschrift fur Physikalische Chemie
IS - 7
ER -