Εξειδίκευση τύπου :	Άρθρο σε επιστημονικό περιοδικό
Τίτλος:	Theoretical modelling of photoswitching of hyperpolarisabilities in ruthenium complexes
Δημιουργός/Συγγραφέας:	Coe B.J. Avramopoulos A. [EL] Παπαδόπουλος, Μάνθος Γ.[EN] Papadopoulos, Manthos G. Pierloot K. Vancoillie S. [EL] Ραϊς, Χεριμπέρτ[EN] Reis, Heribert
Εκδότης:	Wiley-VCH Verlag
Ημερομηνία:	2013
Γλώσσα:	Αγγλικά
ISSN:	0947-6539
DOI:	10.1002/chem.201301380
Άλλο:	PubMed ID: 24123546
Περίληψη:	Static excited-state polarisabilities and hyperpolarisabilities of three RuII ammine complexes are computed at the density functional theory (DFT) and several correlated ab initio levels. Most accurate modelling of the low energy electronic absorption spectrum is obtained with the hybrid functionals B3LYP, B3P86 or M06 for the complex [RuII(NH 3)5(MeQ+)]3+ (MeQ +=N-methyl-4,4′-bipyridinium, 3) in acetonitrile. The match with experimental data is less good for [RuII(NH3) 5L]3+ (L=N-methylpyrazinium, 2; N-methyl-4-{E,E-4-(4- pyridyl)buta-1,3-dienyl}pyridinium, 4). These calculations confirm that the first dipole- allowed excited state (FDAES) has metal-to-ligand charge-transfer (MLCT) character. Both the solution and gas-phase results obtained for 3 by using B3LYP, B3P86 or M06 are very similar to those from restricted active-space SCF second-order perturbation theory (RASPT2) with a very large basis set and large active space. However, the time-dependent DFT λmax predictions from the long-range corrected functionals CAM-B3LYP, LC-ωPBE and wB97XB and also the fully ab initio resolution of identity approximate coupled-cluster method (gas-phase only) are less accurate for all three complexes. The ground state (GS) two-state approximation first hyperpolarisability β2SA for 3 from RASPT2 is very close to that derived experimentally via hyper-Rayleigh scattering, whereas the corresponding DFT-based values are considerably larger. The βresponses calculated by using B3LYP, B3P86 or M06 increase markedly as the π-conjugation extends on moving along the series 2→4, for both the GS and FDAES species. All three functionals predict substantial FDAES βenhancements for each complex, increasing with the π-conjugation, up to about sevenfold for 4. Also, the computed second hyperpolarisabilitiesγ generally increase in the FDAES, but the results vary between the different functionals.
Τίτλος πηγής δημοσίευσης:	Chemistry - A European Journal
Τόμος/Κεφάλαιο:	19
Τεύχος:	47
Σελίδες:	15955-15963
Θεματική Κατηγορία:	[EL] Χημεία (Γενικά)[EN] Chemistry (General)
Λέξεις-Κλειδιά:	density functional caclulations molecular switches nonlinear optics ruthenium complexes
Αξιολόγηση από ομότιμους (peer reviewed):	Ναι
Κάτοχος πνευματικών δικαιωμάτων:	© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Όροι και προϋποθέσεις δικαιωμάτων:	All Open Access, Green
Σημειώσεις:	FP7-REGPOT-2009-1; Seventh Framework Programme, FP7: 245866
Εμφανίζεται στις συλλογές:	Ινστιτούτο Χημικής Βιολογίας - Επιστημονικό έργο