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Titolo:
Electron and energy transfer through bridged systems. 9. Toward a priori evaluation of the intermetallic coupling in bis-metal complexes
Autore:
Reimers, JR; Hush, NS;
Indirizzi:
Univ Sydney, Sch Chem, Sydney, NSW 2006, Australia Univ Sydney Sydney NSWAustralia 2006 h Chem, Sydney, NSW 2006, Australia Univ Sydney, Dept Biochem, Sydney, NSW 2006, Australia Univ Sydney SydneyNSW Australia 2006 iochem, Sydney, NSW 2006, Australia
Titolo Testata:
JOURNAL OF PHYSICAL CHEMISTRY A
fascicolo: 16, volume: 103, anno: 1999,
pagine: 3066 - 3072
SICI:
1089-5639(19990422)103:16<3066:EAETTB>2.0.ZU;2-N
Fonte:
ISI
Lingua:
ENG
Soggetto:
TIGHT-BINDING LINKAGES; ASYMPTOTIC BAND-GAP; IONIC SPECTRA; AB-INITIO; BIS(PENTAAMMINERUTHENIUM) COMPLEXES; DISTANCE DEPENDENCE; EXCITED-STATES; PORPHYRIN; POLYENES; WATER;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
45
Recensione:
Indirizzi per estratti:
Indirizzo: Reimers, JR Univ Sydney, Sch Chem, Sydney, NSW 2006, Australia Univ Sydney Sydney NSW Australia 2006 ey, NSW 2006, Australia
Citazione:
J.R. Reimers e N.S. Hush, "Electron and energy transfer through bridged systems. 9. Toward a priori evaluation of the intermetallic coupling in bis-metal complexes", J PHYS CH A, 103(16), 1999, pp. 3066-3072

Abstract

It is now commonplace to perform a priori calculations using either density functional or ab initio theory for intramolecular electron-transfer coupling strengths within organic molecules, but generally applicable a priori schemes for intermetallic couplings are yet to be determined. We examine thereasons for this, predominantly the need to treat solvent effects within the calculation, shortcomings of, or the unavailability of, Koopmans' theorem (i.e., the need for configuration interaction), and the difficulty of correctly determining ligand orbital band gaps and positioning metal orbitals within them. In particular, we model the observed intermetallic coupling inthe alpha,omega-dipyridylpolyene-bridged ruthenium pentaammine series designed by Woitellier, Launay, and Spangler. After appropriately positioning the metal and ligand orbitals, couplings calculated using Fock matrices are found to be within 25% of experimental values. However,they attenuate too rapidly with increasing bridge length. Use of B3LYP Kohn-Sham matrices as replacements of Fock matrices yields much poorer results, however; the predicted coupling is too strong and even increases for very long bridge lengths.

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Documento generato il 04/12/20 alle ore 01:37:17