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Titolo:
Second ionization energies of gaseous iron oxides and hydroxides: The FeOmHn2+ dications (m=1, 2; n <= 4)
Autore:
Schroder, D; Barsch, S; Schwarz, H;
Indirizzi:
Tech Univ Berlin, Inst Organ Chem, D-10623 Berlin, Germany Tech Univ Berlin Berlin Germany D-10623 an Chem, D-10623 Berlin, Germany
Titolo Testata:
JOURNAL OF PHYSICAL CHEMISTRY A
fascicolo: 21, volume: 104, anno: 2000,
pagine: 5101 - 5110
SICI:
1089-5639(20000601)104:21<5101:SIEOGI>2.0.ZU;2-V
Fonte:
ISI
Lingua:
ENG
Soggetto:
TRANSITION-METAL CATIONS; MULTIPLY-CHARGED IONS; FAST-ATOM-BOMBARDMENT; GAS-PHASE OXIDATION; FOCK HYBRID METHODS; BINDING-ENERGIES; REDOX PROPERTIES; MONATOMIC IONS; BARE FEO+; GENERATION;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
48
Recensione:
Indirizzi per estratti:
Indirizzo: Schwarz, H Tech Univ Berlin, Inst Organ Chem, Str 17 Juni 135, D-10623 Berlin, Germany Tech Univ Berlin Str 17 Juni 135 Berlin Germany D-10623 ermany
Citazione:
D. Schroder et al., "Second ionization energies of gaseous iron oxides and hydroxides: The FeOmHn2+ dications (m=1, 2; n <= 4)", J PHYS CH A, 104(21), 2000, pp. 5101-5110

Abstract

The energetics of selected dicationic iron oxides and hydroxides FeOmHn2+ (m = 1, 2; n less than or equal to 4) are probed by charge-stripping mass spectrometry in conjunction with ab initio calculations employing the B3LYP/6-311+G* level of theory. Specifically, Fe+, FeO+, FeOH+, Fe(H2O)(+), [Fe,O-2,H-2](+), (H2O)FeOH+, and Fe(H2O)(2+) and their respective dications are examined. In most cases, reasonable agreement between experiment and theoryis found, and discrepancies can be attributed to interferences in the experimental study. Nevertheless, some shortcomings of the theoretical approachare obvious. Combination of experimental and theoretical results leads to adiabatic ionization energies of the monocationic iron compounds: IEa(FeO+)= 18.3 +/- 0.4 eV, IEa(FeOH+) = 17.0 +/- 0.4 eV: IEa(Fe(H2O)(+)) = 14.3 +/- 0.5 eV, IEa((H2O)FeOH+) = 15.6 +/- 0.5 eV, and IEa(Fe(H2O)(2)(+)) = 12.6 /- 0.4 eV. In the case of [Fe,O-2,H-2](+), structural isomerism and isobaric interferences give rise to a composite charge-stripping peak and preventthe experimental determination of the ionization energy. Interestingly, the computational results suggest a reversed order of stabilities for the mono- and dicationic [Fe,O-2,H-2](+/2+) isomers, i.e., Fe(OH)(2)(+) > (H2O)FeO > Fe(H2O2)(+) versus Fe(H2O2)(2+) > (H2O)FeO2+ > Fe(OH)(2)(2+). The ion energetics are used to assess the effects of ligation on the stabilities of the iron dications. While the covalent Fe-O and Fe-OH bonds decrease with increasing oxidation state of the metal, the interactions with water are dominated by electrostatic contributions. On average, solvation by water lowers the second ionization energy of the iron compounds studied by as much as 1.6 +/- 0.3 eV.

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Documento generato il 22/09/20 alle ore 23:35:10