Geometrical and optical benchmarking of copper(II) guanidine-quinoline complexes : insights from TD-DFT and many-body perturbation theory (part II)
Copyright © 2014 Wiley Periodicals, Inc.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 35(2014), 29 vom: 05. Nov., Seite 2146-61 |
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| Weitere Verfasser: | , , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2014
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article Research Support, Non-U.S. Gov't TD-DFT copper guanidine ligand-to-metal charge-transfer many-body perturbation theory Coordination Complexes Quinolines Copper mehr... |
| Zusammenfassung: | Copyright © 2014 Wiley Periodicals, Inc. Ground- and excited-state properties of copper(II) charge-transfer systems have been investigated starting from density-functional calculations with particular emphasis on the role of (i) the exchange and correlation functional, (ii) the basis set, (iii) solvent effects, and (iv) the treatment of dispersive interactions. Furthermore (v), the applicability of TD-DFT to excitations of copper(II) bis(chelate) charge-transfer systems is explored by performing many-body perturbation theory (GW + BSE), independent-particle approximation and ΔSCF calculations for a small model system that contains simple guanidine and imine groups. These results show that DFT and TD-DFT in particular in combination with hybrid functionals are well suited for the description of the structural and optical properties, respectively, of copper(II) bis(chelate) complexes. Furthermore, it is found an accurate theoretical geometrical description requires the use of dispersion correction with Becke-Johnson damping and triple-zeta basis sets while solvent effects are small. The hybrid functionals B3LYP and TPSSh yielded best performance. The optical description is best with B3LYP, whereby heavily mixed molecular transitions of MLCT and LLCT character are obtained which can be more easily understood using natural transition orbitals. An natural bond orbital analysis sheds light on the donor properties of the different donor functions and the intraguanidine stabilization during coordination to copper(I) and (II) |
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| Beschreibung: | Date Completed 28.05.2015 Date Revised 30.07.2015 published: Print-Electronic ErratumIn: J Comput Chem. 2015 Feb 5;36(4):272 Citation Status MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.23740 |