TY  - JOUR
A1  - Bois, Juliana
A1  - Koerzdoerfer, Thomas
T1  - Size-Dependence of Nonempirically Tuned DFT Starting Points for G(0)W(0) Applied to pi-Conjugated Molecular Chains
JF  - Journal of chemical theory and computation
N2  - G(0)W(0) calculations for predicting vertical ionization potentials (IPs) and electron affinities of molecules and clusters are known to show a significant dependence on the density functional theory (DFT) starting point. A number of nonempirical procedures to find an optimal starting point have been proposed, typically based on tuning the amount of HF exchange in the underlying hybrid functional specifically for the system at hand. For the case of pi-conjugated molecular chains, these approaches lead to a significantly different amount of HF exchange for different oligomer sizes. In this study, we analyze if and how strongly this size dependence affects the ability of nonempirical tuning approaches to predict accurate IPs for pi-conjugated molecular chains of increasing chain length. To this end, we employ three different nonempirical tuning procedures for the G(0)W(0) starting point to calculate the IP of polyene oligomers up to 22 repeat units and compare the results to highly accurate coupled-cluster calculations. We find that, despite its size dependence, using an IP-tuned hybrid functional as a starting point for G(0)W(0) yields excellent agreement with the reference data for all chain lengths.
Y1  - 2017
U6  - https://doi.org/10.1021/acs.jctc.7b00557
SN  - 1549-9618
SN  - 1549-9626
VL  - 13
SP  - 4962
EP  - 4971
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Brietzke, Thomas Martin
A1  - Dietz, Thomas
A1  - Kelling, Alexandra
A1  - Schilde, Uwe
A1  - Bois, Juliana
A1  - Kelm, Harald
A1  - Reh, Manuel
A1  - Schmitz, Markus
A1  - Koerzdoerfer, Thomas
A1  - Leimkühler, Silke
A1  - Wollenberger, Ulla
A1  - Krueger, Hans-Joerg
A1  - Holdt, Hans-Jürgen
T1  - The 1,6,7,12-Tetraazaperylene Bridging Ligand as an Electron Reservoir and Its Disulfonato Derivative as Redox Mediator in an Enzyme-Electrode Process
JF  - Chemistry - a European journal
N2  - The homodinuclear ruthenium(II) complex [{Ru(l-N4Me2)}(2)(-tape)](PF6)(4) {[1](PF6)(4)} (l-N4Me2=N,N-dimethyl-2,11-diaza[3.3](2,6)-pyridinophane, tape=1,6,7,12-tetraazaperylene) can store one or two electrons in the energetically low-lying * orbital of the bridging ligand tape. The corresponding singly and doubly reduced complexes [{Ru(l-N4Me2)}(2)(-tape(.-))](PF6)(3) {[2](PF6)(3)} and [{Ru(l-N4Me2)}(2)(-tape(2-))](PF6)(2) {[3](PF6)(2)}, respectively, were electrochemically generated, successfully isolated and fully characterized by single-crystal X-ray crystallography, spectroscopic methods and magnetic susceptibility measurements. The singly reduced complex [2](PF6)(3) contains the -radical tape(.-) and the doubly reduced [3](PF6)(2) the diamagnetic dianion tape(2-) as bridging ligand, respectively. Nucleophilic aromatic substitution at the bridging tape in [1](4+) by two sulfite units gave the complex [{Ru(l-N4Me2)}(2){-tape-(SO3)(2)}](2+) ([4](2+)). Complex dication [4](2+) was exploited as a redox mediator between an anaerobic homogenous reaction solution of an enzyme system (sulfite/sulfite oxidase) and the electrode via participation of the low-energy *-orbital of the disulfonato-substituted bridging ligand tape-(SO3)(2)(2-) (E-red1=-0.1V versus Ag/AgCl/1m KCl in water).
KW  - electrochemistry
KW  - enzyme catalysis
KW  - N-ligands
KW  - redox-active ligands
KW  - ruthenium
Y1  - 2017
U6  - https://doi.org/10.1002/chem.201703639
SN  - 0947-6539
SN  - 1521-3765
VL  - 23
SP  - 15583
EP  - 15587
PB  - Wiley-VCH
CY  - Weinheim
ER  -