ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The mechanism of short-time charge delocalization in Hen+ clusters, n=3, 14, 40, and 112, is studied using time-dependent wave packets for the electronic states for fixed nuclear positions chosen randomly from quantum Monte Carlo distributions for the neutral clusters. A DIM (diatomics-in-molecules) potential is used to calculate electronic eigenvalues and eigenvectors for the positively charged clusters, and a coherent superposition of states is created to initially localize the charge on a single atom. The charge distribution as a function of time is then calculated by propagating the initial wave function for 200 fs, during which little nuclear motion will occur. The charge motion is separated into three categories. For initial ionization of relatively isolated atoms in the cluster, the charge is only weakly coupled to other atoms, and there is little charge motion in 200 fs. For initial positions at which two or three atoms are coupled, but isolated from the rest of the cluster, the charge resonates among these atoms. For initial ionization positions at which more than three atoms are coupled, the charge can effectively delocalize over that part of the cluster. For the first two types of positions, which tend to occur near the surface of the cluster, He2+ is likely to form and the cluster will fragment before significant charge migration can occur. Charge delocalization tends to occur for initial ionization at the third type of location in the core of the cluster. For the initial positions that lead to charge delocalization, the distance and direction of the delocalization was characterized. © 1998 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.477784
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