| Online-Ressource |
Verfasst von: | Cui, Zhong-hua [VerfasserIn]  |
| Lischka, Hans [VerfasserIn]  |
| Müller, Thomas [VerfasserIn]  |
| Plasser, Felix [VerfasserIn]  |
| Kertesz, Miklos [VerfasserIn]  |
Titel: | Study of the diradicaloid character in a prototypical pancake-bonded dimer |
Titelzusatz: | the stacked tetracyanoethylene (TCNE) anion dimer and the neutral K2TCNE2 complex |
Verf.angabe: | Zhong-hua Cui, Hans Lischka, Thomas Mueller, Felix Plasser, Miklos Kertesz |
Jahr: | 2014 |
Jahr des Originals: | 2013 |
Umfang: | 12 S. |
Fussnoten: | Im Titel ist die Zahl "2" jeweils tiefgestellt ; Published online on November 20, 2013 ; Gesehen am 14.10.2020 |
Titel Quelle: | Enthalten in: ChemPhysChem |
Ort Quelle: | Weinheim : Wiley-VCH Verl., 2000 |
Jahr Quelle: | 2014 |
Band/Heft Quelle: | 15(2014), 1, Seite 165-176 |
ISSN Quelle: | 1439-7641 |
Abstract: | The π-bonded tetracyanoethylene anion dimer (TCNE22−) and the neutral K2TCNE2 system have been investigated to obtain new insights into the unique features of two-electron multicenter (2e-mc) π-pancake bonding. The inter-radical interaction leads to a significant diradicaloid character described by two singly occupied molecular orbitals (SOMOs) of the monomers. A highly correlated approach, the multireference averaged quadratic coupled-cluster (MR-AQCC) method, has been used to achieve a balanced description of the different types of electron correlation that occur in this system. The analysis of the interaction energies for the two systems in the singlet and the lowest triplet states and of the unpaired electron densities demonstrate the importance of diradical π bonding in addition to the conventional van der Waals interactions that occur in intermolecular interactions. In this analysis, the separation of the repulsive Coulomb interaction energies from the remaining terms turned out to be a crucial prerequisite to achieve consistent results. Our calculations also confirm that the driving force behind the energetic stability of the pancake bonds predominantly derives from the overlap of the SOMO-SOMO bonding interaction. |
DOI: | doi:10.1002/cphc.201300784 |
URL: | Bitte beachten Sie: Dies ist ein Bibliographieeintrag. Ein Volltextzugriff für Mitglieder der Universität besteht hier nur, falls für die entsprechende Zeitschrift/den entsprechenden Sammelband ein Abonnement besteht oder es sich um einen OpenAccess-Titel handelt.
Volltext: https://doi.org/10.1002/cphc.201300784 |
| Volltext: https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/cphc.201300784 |
| DOI: https://doi.org/10.1002/cphc.201300784 |
Datenträger: | Online-Ressource |
Sprache: | eng |
Sach-SW: | bond theory |
| density functional theory calculations |
| pancake bonding |
| radical ions |
| stacking interactions |
K10plus-PPN: | 1735498467 |
Verknüpfungen: | → Zeitschrift |
Study of the diradicaloid character in a prototypical pancake-bonded dimer / Cui, Zhong-hua [VerfasserIn]; 2014 (Online-Ressource)