A new synthetic approach, reacting alkaline earth metal iodides with butyllithium, lithium hydroxide, and/or lithium butoxide under salt elimination, is presented, giving access to some interesting clusters of calcium, strontium, and barium, partially in combination with lithium. The so far largest calcium cluster Li[{Ca₇(μ₃-OH)₈I₆(thf)₁₂}₂(μ₂-I)]·3THF, 4, and the new strontium compound [Sr₃I₃(OH)₂(thf)₉]I, 5, are shown to feature common building blocks of OH-capped M₃ triangles. On the basis of mainly electrostatic interactions, these clusters are not volatile. By introducing LiO^tBu, the two clusters [IM(O^tBu)₄{Li(thf)}₄(OH)] (6, M = Sr; 7, M = Ba) are prepared, 7 exhibiting volatility as an important physical property, which makes it a potential precursor for chemical vapor deposition. The structural relationship between 4, 5, 6, and 7 and their respective starting materials is shown, and possible reaction mechanisms are proposed. Exhibiting surprising and new structural motifs, the bonding modes of these clusters are investigated by the electron localization function as well as by ab initio calculations.

The adsorption of methanol on V₂O₅ and its mild oxidation to formaldehyde has been studied applying density functional theory. The model used throughout is a cluster model saturated by hydrogen atoms. It is shown that the adsorption of methanol is energetically favored if the cluster is partially reduced (i.e., protonated because of the dissociative adsorption of water). Methanol behaves as a soft base and adsorbs as a methoxonium cation. The proposed mechanism is based on two steps, the first being the dissociation of methanol to form a methoxy group on the surface. This dissociation occurs between the oxygen and the carbon atoms of methanol. Finally, for the second step, which corresponds to the desorption of formaldehyde, the calculations show that filling of the vanadyl oxygen vacancy created by formaldehyde desorption is crucial to cope with an energetically feasible reaction pathway.

The absorption and emission spectra of benzo[g,h,i]perylene, a six ring polycyclic aromatic hydrocarbon molecule (C₂₂H₁₂), embedded in a rare gas matrix are reported. Time dependent emission shows that this molecule exhibits sharp phosphorescence in the red. Supporting theoretical calculations using the recently developed time-dependent density-functional response theory formalism (TD–DFRT) allow a tentative assignment for the observed transitions. The astrochemical significance of the results is briefly discussed.

Nitrosyl metal complexes, such as the sodium nitroprusside, have attracted chemists' interest for more than 30 years. The existence of long-lived metastable states easily populated by irradiation are the principal reason for this interest. Those long-lived states are interesting either for technical applications or for fundamental research. In this work, we present a comparative density functional theory (DFT) study of the ground state of two different nitrosyl compounds:  sodium nitroprusside and cyclopentadienylnitrosylnickel(II).

The photochemical reactions of the nitroprusside and the CpNiNO complexes are explained on the basis of ΔSCF and time-dependent density functional theory (TD-DFT) calculations. Both similarities and differences in the photochemical processes are highlighted.

The photochemistry of the CpNiNO complex has been investigated using density functional theory. The whole potential energy curve along the NiNO angle coordinate is presented for the first time with both ground and metastable states, and transition states connecting the minima. The excited states of the GS, MS_I, and MS_II species have been calculated using time-dependent density functional theory. Furthermore, the structure of the excited states pertaining to the photochemistry of CpNiNO has been optimized. From these results it is shown that the backward GS � MS_II � MS_I reaction is more efficient than the forward GS → MS_II → MS_I scheme.

Vertical excitations calculated for the CrO₄^2- , MnO₄^2-  , RuO₄, CrF₆, FeCp₂, RuCp₂ and CpNiNO species are compared to experimental spectra. The results obtained from the time-dependent density-functional theory−response theory (TD-DFRT) method are compared to both previously reported ΔSCF calculations and experiment. The results show that, in general, excited states of metal oxide and metallocene compounds are well described by TD-DFRT. However, serious difficulties are met with the CrF₆ system.