We present a combined density functional/time-dependent density functional study of the electronic structure and optical absorption spectrum of the charge-transfer sensitizer cis-[Ru(4,4'-COOH-2,2'-bpY)(2)(NCS)(2)] in water solution. To simulate the effect of different pH values, calculations have been performed for both the title complex and the corresponding tetra-deprotonated species, cis-[Ru(4,4'-COO-2,2'-bPY)(2)(NCS)(2)](4-). The experimentally observed blue-shift of the spectrum at high pH is well reproduced by our theoretical model and appears to be related to destabilization of the bipyridines pi(*) LUMOs as a result of the increased electron density on the deprotonated carboxylic groups. (C) 2004 Elsevier B.V. All rights reserved.

Time-dependent density functional theory study of the absorption spectrum of [Ru(4,4′-COOH-2,2′-bpy)2(NCS)2] in water solution: Influence of the pH

De Angelis, Filippo
;
Selloni, Annabella
2004

Abstract

We present a combined density functional/time-dependent density functional study of the electronic structure and optical absorption spectrum of the charge-transfer sensitizer cis-[Ru(4,4'-COOH-2,2'-bpY)(2)(NCS)(2)] in water solution. To simulate the effect of different pH values, calculations have been performed for both the title complex and the corresponding tetra-deprotonated species, cis-[Ru(4,4'-COO-2,2'-bPY)(2)(NCS)(2)](4-). The experimentally observed blue-shift of the spectrum at high pH is well reproduced by our theoretical model and appears to be related to destabilization of the bipyridines pi(*) LUMOs as a result of the increased electron density on the deprotonated carboxylic groups. (C) 2004 Elsevier B.V. All rights reserved.
2004
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11391/1442796
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 132
  • ???jsp.display-item.citation.isi??? 128
social impact