RESUMO
The manganese-oxo "cubane" core complex Mn(4)O(4)L(1)(6) (1, L(1) = Ph(2)PO(2-)), a partial model of the photosynthetic water oxidation site, was shown previously to undergo photodissociation in the gas phase by releasing one phosphinate anion, an O(2) molecule, and the intact butterfly core cation (Mn(4)O(2)L(1)(5+)). Herein, we investigate the photochemistry and electronic structure of a series of manganese-oxo cubane complexes: [Mn(4)O(4)L(2)(6)] (2), 1(+)(ClO(4-)), 2(+)(ClO(4-)), and Mn(4)O(3)(OH)L(1)(6) (1H). We report the atomic structure of [Mn(4)O(4)L(2)(6)](ClO(4)), 2(+)(ClO(4-)) [L(2) = (4-MeOPh)(2)PO(2-)]. UV photoexcitation of a charge-transfer band dissociates one phosphinate, two core oxygen atoms, and the Mn(4)O(2)L(5)(+) butterfly as the dominant (or exclusive) photoreaction of all cubane derivatives in the gas phase, with relative yields: 1H >> 2 > 1 > 2(+) > 1(+). The photodissociation yield increases upon (1) reducing the core oxidation state by hydrogenation of a corner oxo (1H), (2) increasing the electron donation from the phosphinate ligand (L(2)), and (3) reducing the net charge from +1 to 0. The experimental Mn-O bond lengths and Mn-O bond strengths and the calculated ligand binding energy explain these trends in terms of weaker binding of phosphinate L(2) versus L(1) by 14.7 kcal/mol and stronger Mn-(mu(3)-O)(core) bonds in the oxidized complexes 2(+) and 1(+) versus 2 and 1. The calculated electronic structure accounts for these trends in terms of the binding energy and antibonding Mn-O(core) and Mn-O'(ligand) character of the degenerate highest occupied molecular orbital (HOMO), including (1) energetic destabilization of the HOMO of 2 relative to 1 by 0.75 eV and (2) depopulation of the antibonding HOMO and increased ionic binding in 1(+) and 2(+) versus 1 and 2.
Assuntos
Manganês/química , Compostos Organometálicos/química , Oxigênio/química , Simulação por Computador , Elétrons , Manganês/efeitos da radiação , Modelos Químicos , Conformação Molecular , Compostos Organometálicos/efeitos da radiação , Oxirredução , Oxigênio/efeitos da radiação , Fotoquímica , Estereoisomerismo , Raios UltravioletaRESUMO
The behavior of single crystals of NaCl: Ca(2+), Mn(2+) exposed to gamma rays was explored for its potential usage as a dosimeter. The study was focused to the effect of dose and dose rate. The crystals were analyzed using thermoluminescence (TL). The productions of irradiation defects in the solid were correlated with the glow curve. F-centers were measured as function of the dose. The bleaching of the F-centers produced a decrease of the peak of the glow curve. The results showed that the response is linear in an interval up to 60 Gy.
Assuntos
Raios gama , Radiometria/métodos , Cálcio/efeitos da radiação , Cristalização , Manganês/efeitos da radiação , Radiometria/instrumentação , Cloreto de Sódio/efeitos da radiaçãoRESUMO
The dosimetry of beta radiation is a difficult process especially because of the low penetration of beta particles in matter. The dosemeter utilised for this kind of procedure needs to approximate an ideal point-like detector: it should be as thin as possible, and its area should be small. The thermoluminescence dosemeters (TLDs) meet with these requirement properties. The aim of this work was to study the dosimetric characteristics of different TLDs to verify the possibility of their use for the calibration of 90Sr+90Y plane applicators. The response reproducibility, calibration curves, TL response as a function of the source-detector distance, the transmission factors and the linearity of the sample response were obtained for several types of dosimetric pellets.