A theoretical study of the gas-phase chemiionization reactions La+O and La+O2

The La + O and La + O2 chemiionization reactions have been investigated with quantum chemical methods. For La + O2(X3?g) and La + O2(a1?g), the chemiionization reaction La + O2 ? LaO2+ + e? has been shown to be endothermic and does not contribute to the experimental chemielectron spectra. For the La + O2(X3?g) reaction conditions, chemielectrons are produced by La + O2 ? LaO + O, followed by La + O ? LaO+ + e?. This is supported by the same chemielectron band, arising from La + O ? LaO+ + e?, being observed from both the La + O(3P) and La + O2(X3?g) reaction conditions. For La + O2(a1?g), a chemielectron band with higher electron kinetic energy than that obtained from La + O2(X3?g) is observed. This is attributed to production of O(1D) from the reaction La + O2(a1?g) ? LaO + O(1D), followed by chemiionization via the reaction La + O(1D) ? LaO+ + e?. Potential energy curves are computed for a number of states of LaO, LaO* and LaO+ to establish mechanisms for the observed La + O ? LaO+ + e? chemiionization reactions

Rationalization of the Lanthanide-Ion-Driven Magnetic Properties in a Series of 4f–5d Cyano-Bridged Chains

Magnetic properties of new d-f cyanido-bridged 1D assemblies [RE(pzam)3(H2O)W(CN)8]·H2O (RE(III) = Gd, 1, Tb, 2, Dy, 3; pzam = pyrazine-2-carboxamide) were studied by temperature- and field-dependent magnetization measurements. No evidence for 3D interchain magnetic ordering is found above 2 K. Multiconfiguration ab initio calculations and subsequent modeling afforded simulation of the weak zero-field splitting effect in 1 and discussion of magnetic anisotropy in the f units of compounds 2 and 3. A semiquantitative corroboration with the experimental magnetic measurements is presented, performing the simulation of magnetic susceptibility vs temperature and magnetization vs field variation. The association into molecular and supramolecular architectures is analyzed by means of energy decomposition subsequent to the DFT calculations on idealized molecular models extracted from the experimental chain structure.<br/