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Titolo:
SOLVENT EFFECTS ON MOLECULAR AND IONIC SPECTRA .5. DEVELOPMENT OF A METHOD FOR SIMULATION OF THE LIQUID STRUCTURE AND SOLVATOCHROMIC SHIFT OF INORGANIC COMPLEXES SUCH AS PENTAAMINOPYRIDYLRUTHENIUM(II) IN WATER
Autore:
ZENG J; HUSH NS; REIMERS JR;
Indirizzi:
UNIV SYDNEY,DEPT PHYS & THEORET CHEM SYDNEY NSW 2006 AUSTRALIA UNIV SYDNEY,DEPT PHYS & THEORET CHEM SYDNEY NSW 2006 AUSTRALIA UNIV SYDNEY,DEPT BIOCHEM SYDNEY NSW 2006 AUSTRALIA
Titolo Testata:
Journal of physical chemistry
fascicolo: 26, volume: 99, anno: 1995,
pagine: 10459 - 10470
SICI:
0022-3654(1995)99:26<10459:SEOMAI>2.0.ZU;2-7
Fonte:
ISI
Lingua:
ENG
Soggetto:
TRANSITION-METAL COMPLEXES; DIFFERENTIAL-OVERLAP TECHNIQUE; ENERGY PERTURBATION-METHODS; MONTE-CARLO CALCULATIONS; ELECTRON-TRANSFER; INTERMEDIATE NEGLECT; REACTION-FIELD; BIS(PENTAAMMINERUTHENIUM) COMPLEXES; POTENTIAL FUNCTIONS; DILUTE PYRIMIDINE;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Science Citation Index Expanded
Citazioni:
83
Recensione:
Indirizzi per estratti:
Citazione:
J. Zeng et al., "SOLVENT EFFECTS ON MOLECULAR AND IONIC SPECTRA .5. DEVELOPMENT OF A METHOD FOR SIMULATION OF THE LIQUID STRUCTURE AND SOLVATOCHROMIC SHIFT OF INORGANIC COMPLEXES SUCH AS PENTAAMINOPYRIDYLRUTHENIUM(II) IN WATER", Journal of physical chemistry, 99(26), 1995, pp. 10459-10470

Abstract

Our method (parts 1-3) for estimating solvent effects on electronic spectra in media with strong solute-solvent interactions is extended tointerpret the MLCT absorption spectrum of Ru2+(NH3)(5)-pyridine in dilute aqueous solution: it should be generally applicable to inorganic charge-transfer spectra. First, both ab initio MCSCF and INDO/S-CI methods are used to estimate the gas-phase electronic excitation energiesand state charge distributions; second, Monte Carlo simulations are performed to determine the ground-state liquid structure; finally the solvent shift is evaluated based on the gas-phase charge distributions and the explicit ground state solvent structure: no arbitrarily adjustable parameters such as ''cavity radii'' are required. Several intermolecular potential surfaces are used to investigate the relationship between solvent shift and solvent structure, with the most reasonable structure determined by comparison with results simulated for dilute Ru2- (NH3)(6) solution: for this complex, the inner solvent shell contained 13 water molecules which formed 18 hydrogen bonds to the ammonia ligands. The solvent shift calculated using various methods is -7500 +/- 1500 cm(-1), implying that the gas-phase transition energy should be32000 +/- 1500 cm(-1), consistent, given the level of approximation used, with the INDO/S-CI and ab initio MCSCF predictions which range from 34 000 to 39 000 cm(-1). It is proposed that a method which is bothpracticable and reliable for calculations such as this is to use ab initio SCF ESP charges combined with Kollman's force field as the intermolecular potential during the simulations and to use INDO/S-CI charges when evaluating solvent shifts.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 02/12/20 alle ore 14:58:51