Catalogo Articoli (Spogli Riviste)

OPAC HELP

Titolo:
SOLVENT EFFECTS ON MOLECULAR AND IONIC SPECTRA .4. PHOTOCHEMISTRY OF FE2- POSSIBLE MECHANISMS FOR THE PRIMARY ABSORPTION PROCESS LEADING TOELECTRON EJECTION((H2O)(6) IN WATER REVISITED )
Autore:
ZENG J; CRAW JS; HUSH NS; REIMERS JR;
Indirizzi:
UNIV SYDNEY,DEPT PHYS & THERORET CHEM SYDNEY NSW 2006 AUSTRALIA UNIV SYDNEY,DEPT PHYS & THERORET CHEM SYDNEY NSW 2006 AUSTRALIA UNIV SYDNEY,DEPT BIOCHEM SYDNEY NSW 2006 AUSTRALIA
Titolo Testata:
Journal of physical chemistry
fascicolo: 43, volume: 98, anno: 1994,
pagine: 11075 - 11088
SICI:
0022-3654(1994)98:43<11075:SEOMAI>2.0.ZU;2-7
Fonte:
ISI
Lingua:
ENG
Soggetto:
TRANSITION-METAL COMPLEXES; MONTE-CARLO SIMULATIONS; DIFFERENTIAL-OVERLAP TECHNIQUE; CHARGE-TRANSFER; COMPUTER-SIMULATIONS; INTERMEDIATE NEGLECT; HYDRATED ELECTRON; REACTION-FIELD; LIQUID WATER; BIS(PENTAAMMINERUTHENIUM) COMPLEXES;
Tipo documento:
Review
Natura:
Periodico
Settore Disciplinare:
Science Citation Index Expanded
Citazioni:
143
Recensione:
Indirizzi per estratti:
Citazione:
J. Zeng et al., "SOLVENT EFFECTS ON MOLECULAR AND IONIC SPECTRA .4. PHOTOCHEMISTRY OF FE2- POSSIBLE MECHANISMS FOR THE PRIMARY ABSORPTION PROCESS LEADING TOELECTRON EJECTION((H2O)(6) IN WATER REVISITED )", Journal of physical chemistry, 98(43), 1994, pp. 11075-11088

Abstract

Our method (parts I-III1-3) for estimating solvent shifts of species which have strong specific interactions (e.g., hydrogen bonding) with the solvent is applied to inorganic charge transfer spectra; As the simulation of the structure of ions in solution is not completely straightforward, a number of aspects of the simulation procedure are investigated, concentrating on solvent shift sensitivity. Specifically, we investigate the ultraviolet absorption spectrum of aqueous Fe2+(H2O)(6);for centrosymmetric systems such as this, it is found to be most important to correctly represent the structure of the second coordination shell. Assumptions such as that of rigidity of the inner shell and theparticular choice of boundary conditions are of minor consequence. Ina process studied extensively over several decades, ultraviolet lightabsorption results in electron ejection, leading to the photochemicaldecomposition of water. Several mechanisms for the primary process have been suggested in the past, without consensus being achieved. Theseinclude initial metal to ligand charge transfer (MLCT), metallic 3d --> 4s absorption, direct electron photodetachment producing a partially solvated electron in a preexisting solvent cavity, and charge transfer to solvent absorption (CTTS). We consider the energetics and solvent shift of the first three of these processes, concluding that the MLCT band is too high in energy, the d --> s band could participate, and the photodetachment band is at the correct energy and intensity to account for all that is (as yet) observed of the absorption band. In general, a rather complicated picture of this process in inorganic complexes emerges.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 02/12/20 alle ore 15:15:46