Structural Characterization of Unprecedented Al<sub>14</sub>O<sup>–</sup> and Al<sub>15</sub>O<sub>2</sub><sup>–</sup>: Photoelectron Spectroscopy and Density Functional
Calculations
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Abstract
New aluminum oxide clusters Al<sub>14</sub>O<sup>–</sup> and Al<sub>15</sub>O<sub>2</sub><sup>–</sup> were observed
unprecedentedly in the gas-phase reaction of Al<sub><i>n</i></sub><sup>–</sup> and O<sub>2</sub>. Photoelectron spectroscopic
measurements and density functional calculations indicated that Al<sub>14</sub>O<sup>–</sup> and Al<sub>15</sub>O<sub>2</sub><sup>–</sup> are composed of an icosahedral Al<sub>13</sub> moiety
bonded by one and two OAl unit(s), respectively. The preferential
formation of Al<sub>14</sub>O<sup>–</sup> and Al<sub>15</sub>O<sub>2</sub><sup>–</sup> is explained in terms of the high
stability associated with the Al<sub>13</sub> moiety and efficient
collisional trapping as intermediates of oxidative etching reactions