Record Details

Role of electronic structure of ruthenium polypyridyl dyes in the photoconversion efficiency of dye-sensitized solar cells: Semiempirical investigation

DSpace at IIT Bombay

View Archive Info
 
 
Field Value
 
Title Role of electronic structure of ruthenium polypyridyl dyes in the photoconversion efficiency of dye-sensitized solar cells: Semiempirical investigation
 
Creator SRIKANTH, K
MARATHE, VR
MISHRA, MK
 
Subject molecular-orbital calculations
differential-overlap technique
transition-metal complexes
titanium-dioxide films
x = cl
nanocrystalline tio2
intermediate neglect
excited-state
charge separation
crystal-structure
dyes
electronic structure
photoconversion
ruthenium
zindo/s
 
Description ZINDO/S calculations on cis-Ru(4,4'-dicarboxy-2,2'-bipyridine)2(X)2 and cis-Ru(5,5'-dicarboxy-2,2'-bipyridine)(2)(X)(2) complexes where X = Cl-, CN-, and NCS- reveal that the highest occupied molecular orbital (HOMO) of these complexes has a large amplitude on both the nonchromophoric ligand X and the central ruthenium atom. The lowest-energy metal to ligand charge transfer (MLCT) transition in these complexes involves electron transfer from ruthenium as well as the halide/pseudohalide ligand to the polypyridyl ligand. The contribution of the halide/pseudohalide ligand(X) to the HOMO affects the total amount of charge transferred to the polypyridyl ligand and hence the photoconversion efficiency. The virtual orbitals involved in the second MLCT transition in 4,4'-dicarboxy-2,2'-bipyridine complexes have higher electron density on the -COOH group compared to the lowest unoccupied molecular orbital and hence a stronger electronic coupling with the TiO2 surface and higher injection efficiency at shorter wavelengths. In comparison, the virtual orbitals involved in the second MLCT transition in 5,5'-dicarboxy-2,2'-bipyridine complexes have lesser electron density on the -COOH group, leading to a weaker electronic coupling with the TiO2 surface and therefore lower efficiency for electron injection at shorter wavelengths for these complexes. (C) 2002 .
 
Publisher JOHN WILEY & SONS INC
 
Date 2011-08-16T13:24:58Z
2011-12-26T12:54:57Z
2011-12-27T05:43:25Z
2011-08-16T13:24:58Z
2011-12-26T12:54:57Z
2011-12-27T05:43:25Z
2002
 
Type Article
 
Identifier INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 89(6), 535-549
0020-7608
http://dx.doi.org/10.1002/qua.10321
http://dspace.library.iitb.ac.in/xmlui/handle/10054/9512
http://hdl.handle.net/10054/9512
 
Language en