01981nas a2200169   4500008004100000022001400041245014900055210006900204260007100273300001600344490000800360520124700368100002501615700002601640700001601666856012901682       2011                        eng d  a1932-744700aSize- and shape-sensitive reactivity behavior of Al-n(n=2-5, 13, 30, and 100) clusters toward the N-2 molecule: a first-principles investigation0 aSize and shapesensitive reactivity behavior of Alnn25 13 30 and   a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcAUG  a14615-146230 v1153 a<p>Reactivity of aluminum clusters has been found to exhibit size-sensitive variations. N-2 reduction is a hard process, and its dissociation on the Al surface is one of the few chemical methods available under nonhazardous conditions. In this context, we attempt to understand the adsorption behavior of N-2 molecules as a function of varying size and shape of Al clusters using a Density Functional Theory (DFT) based method. During the complex formation, various N-2 adsorption modes are examined. The results clearly demonstrate that, while the interaction energy does not vary with respect to the cluster size, shape of the cluster is highly contributive toward the chemisorption (a prerequisite for the reactivity) of the N-2 molecule. The underlying electronic and structural factors influencing the adsorption of N-2 molecules on the Al clusters are analyzed with the help of the Electron Localization Function (ELF) and Frontier Molecular Orbitals. As an illustration, the activation barrier calculations on various Al-13 conformations are calculated, and results confirm the experimental propositions that high-energy structures (depending upon their geometrical and electronic orientation) are more favorable for N-2 reduction.</p>1 aKulkarni, Bhakti, S.1 aKrishnamurty, Sailaja1 aPal, Sourav  uhttps://library.ncl.res.in/content/size-and-shape-sensitive-reactivity-behavior-al-nn2-5-13-30-and-100-clusters-toward-n-2-0