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The interaction of argon with doubly transition metal doped aluminum clusters, AlnTM2+ (n = 1–18, TM = V, Nb, Co, Rh), is studied experimentally in the gas phase via mass spectrometry. Density functional theory calculations on selected sizes are used to understand the argon affinity of the clusters, which differ depending on the transition metal dopant. The analysis is focused on two pairs of consecutive sizes: Al6,7V2+ and Al4,5Rh2+, the largest of each pair showing a low affinity toward Ar. Another remarkable observation is a pronounced drop in reactivity at n = 14, independent of the dopant element. Analysis of the cluster orbitals shows that this feature is not a consequence of cage formation but is electronic in nature. The mass spectra demonstrate a high similarity between the size-dependent reactivity of the clusters with Ar and H2. Orbital interactions provide an intuitive link between the two and further establish the importance of precursor states in the reactions of the clusters with hydrogen. [ABSTRACT FROM AUTHOR]

Interactions between tetracyanoquinodimethane (TCNQ) and two typical silver clusters Ag13 and Ag20 are studied by first-principles DFT calculations. Charge transfer (CT) from silver clusters to TCNQ molecules initiates the Ag–N bond formation at selective sites resulting in the formation of different isomers of Ag13–TCNQ and Ag20–TCNQ complexes. We show here a comprehensive spectroscopic analysis for the two CT complexes on the basis of Raman and infrared activities. Furthermore, frontier molecular orbital (FMO) and natural bond orbital (NBO) analysis of the complexes provides a vivid illustration of electron cloud overlap and interactions. The behavior of TCNQ adsorbed on the tetrahedral Ag20 cluster was even found in good agreement with the experimental measurement of TCNQ molecules on a single-crystal Ag(111) surface. This study not only endeavors to clarify the charge-transfer interactions of TCNQ with silver, but also presents a finding of enhanced charge transfer between Ag13 and TCNQ indicating potential for candidate building blocks of granular materials. [ABSTRACT FROM AUTHOR]

Small cobalt clusters [Formula: see text] and their single chromium atom doped counterparts Co n-1 Cr + (n  =  3-5) were studied mass spectrometrically by measuring the infrared multiple photon dissociation (IRMPD) spectra of the corresponding argon tagged complexes. The geometric and electronic structures of the [Formula: see text] and Co n-1 Cr + (n  =  3-5) clusters as well as their Ar complexes were optimized by density functional theory (DFT) calculations. The obtained lowest energy structures were confirmed by comparing the IRMPD spectra of [Formula: see text] and [Formula: see text] (n  =  3-5, m  =  3 and 4) with the corresponding calculated IR spectra. The calculations reveal that the doped Co n-1 Cr + clusters retain the geometric structures of the most stable [Formula: see text] clusters. However, the coupling of the local magnetic moments within the clusters is altered in a size-dependent way: the Cr atom is ferromagnetically coupled in Co 2 Cr + and Co 3 Cr + , while it is antiferromagnetically coupled in Co 4 Cr + .