Quasiclassical Trajectories and ab initio Potential Energy Calculations for Some Reactions of Metal Atoms with H2
Date Issued
2009
Date
2009
Author(s)
Hsiao, Ming-Kai
Abstract
We study three reaction schemes, M* + H2--> MH + H (M*=Be(21P), Li(22P), and Ca(31D)) to understand the related dynamic properties by quasiclassical trajectory calculations in this work. All of the potential energies of ground and excited state are calculated by HF/CASSCF/MRCI level of ab initio method, and analytically fitted to two new potential energy functions of 1A’ and 2A’. For all reactions, the reaction channel follows a near C2v insertion. We don’t observe any barrier energy in the Be + H2, and the rotational populations are characterized by a bimodal distribution for v=0 and v=1 of BeH product, showing one maximum component around N = 9-11, and the other one peaking at approximately N=29. For the Li + H2, when the H2 bond distance increases, the reaction rate is facilitated. Thus, the rotational population distribution is enhanced by about 85 times at H2(v=1) as compared to H2(v=0). The resulting rotational distributions of LiH are unimodal for both cases of H2(v=1) and H2(v=0). In the reaction of Ca(31D) + H2, the product rotational distribution is also unimodal. The relative angle between orbital angular momentum (l’) and rotational angular momentum (j’) is very small in this reaction, such that most rotation populations lie in the low rotational state.
Subjects
ab initio calculations
quasiclassical trajectories
potential energy surface fitting
Type
thesis
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