We describe electron transfer through the NrfHA nitrite reductase heterodimer using a thermodynamic integration scheme based upon molecular dynamics simulations. From the simulation data, we estimate two of the characteristic energies of electron transfer, the thermodynamic driving forces, ΔG, and the reorganization energies, λ. Using a thermodynamic network analysis, the statistical accuracy of the ΔG values can be enhanced significantly. Although the reaction free energies and activation barriers are hardly affected by protein aggregation, the complete reaction mechanism only emerges from the simulations of the dimer rather than focussing on the individual protein chains: it involves an equienergetic transprotein element of electron storage and conductivity.

We present a computer simulation study of the thermodynamics and kinetics of charge transfer reactions within the fungal peroxidase AauDyPI from Auricularia auriculae-judae. Driving forces and reorganization energies are obtained from a thermodynamic integration scheme based upon molecular dynamics simulations. To enhance the numerical accuracy, the free energies are analyzed within a least-squares scheme of a closely knit thermodynamic network. We identify Tyr147, Tyr229, and Trp105 as oxidative agents, and find Trp377 to be a long-lived reaction intermediate. The results are compared to recent experimental findings.

The chalcogenido indates K6In2Q6 (Q = S, Se, Te) were synthesized from melts of the pure elements at a maximum temperature of 700 °C. All three potassium salts contain dinuclear units [In2Q6]6– of two edge‐sharing [InQ4] tetrahedra. The sulfido and the selenido indate are isotypic and crystallize in the K6Mn2O6‐type structure [monoclinic, space group P21/c, a = 784.32(9)/809.32(3), b = 1274.58(14)/1322.37(4), c = 836.48(9)/870.53(3) pm, β = 97.900(2)/97.5877(8)°, Z = 2, R1 = 0.0123/0.0109; for Q = S/Se]. The tellurido indate K6In2Te6 crystallizes in a new orthorhombic structure type [space group Pnma, a = 1793.70(12), b = 1491.55(11), c = 837.40(6) pm, Z = 4, R1 = 0.0157]. In this structure, the telluride anions form a hexagonal close packing, in which K+ cations occupy all octahedral voids; the In3+ ions take 1/6 (but always adjacent) tetrahedral voids. This structure‐chemical relation to the h.c.p. packing, which is similarly found for most of the sodium dimetallates (e.g. Na6Fe2S6), is substantiated by a full crystallographic group‐subgroup tree. The crystal chemistry of the new indates is discussed and compared with that of alkali chalcogenido metallates(III) of Fe, Al and Ga containing [M2Q6]6– dimers, which overall form as many as ten different structure types. DFT band structure calculations of the three title compounds exhibit bandgaps, which continuously decrease from the S to the Te compound and which are also in accordance with the pale yellow (S), bright yellow (Se) and red‐brown (Te) color of the compounds. The chemical bonding in the salts and within the metallate anion is discussed on the basis of the partial DOS and a Bader analysis of the calculated electron density.

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The six isotypic alkali ortho chalcogenido manganates A6[MnIIQ4] (A=Rb, Cs; Q=S, Se, Te) were synthesized – in most cases in pure phase – from stoichiometric mixtures of the manganese monochalcogenides MnQ, the elemental chalcogens and Rb2S/Cs2S2 (sulfido salts) or the pure alkali elements (selenido and tellurido salts) as alkali sources at maximum temperatures between 650 and 800°C. Their hexagonal crystal structures were refined by means of X-ray single crystal data (space group P63mc, Na6ZnO4-type structure, Z=2; A/Q: Rb/S: a=1019.34(2), c=792.560(10) pm, R1=0.0166; Rb/Se: a=1055.74(2), c=821.14(2) pm, R1=0.0275; Rb/Te: a=1126.68(2), c=860.54(2) pm, R1=0.0152; Cs/S: a=1056.68(2), c=831.22(2) pm, R1=0.0168; Cs/Se: a=1096.04(3), c=858.13(2) pm, R1=0.0194; and Cs/Te: a=1167.72(3), c=896.95(2) pm, R1=0.0140). The chiral structures contain isolated C3 symmetric, but very close to ideal tetrahedral, ortho manganate(II) anions [MnIIQ4]6− with Mn–Q distances of 248.7–250.7 (Q=S), 260.7–263.0 (Q=Se) and 280.0–282.4 pm (Q=Te). The chalcogenide ions form a hexagonal closed packing with slightly puckered 36 nets, in which the A(2) cations occupy 3/4 of the octahedral interstices, whereas Mn takes 1/8 and A(1) 3/8 of the tetrahedral voids. Magnetic measurements on the three Cs compounds showed Curie-Weiss behavior down to a temperature of 1.9 K, with magnetic moments significantly reduced with respect to the expected spin-only value of a d5 ion. The electronic band structures of the four salts (Na/Rb)6Mn(S/Te)4, which were calculated within the GGA+U approach, allow a comparison of the chemical bonding characteristics and the magnetic properties within the alkali cation and the chalcogenido ligand series.