Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

3-2011

Journal or Book Title

Journal of Physical Chemistry A

Volume

115

Issue

13

First Page

2679

Last Page

2691

DOI

10.1021/jp1105778

Abstract

The mechanism and dynamics of the formation of a hydrogen molecule by incorporating two hydrogen atoms in a stepwise manner into the cavity of some POSS (polyhedral oligomeric silsesquioxanes) compounds has been investigated by ab initio molecular orbital and ab initio molecular dynamics (AIMD) methods. The host molecules in the present reactions are two types of POSS, T8 ([HSiO1.5]8) and T12(D2d) ([HSiO1.5]12). AIMD simulations were performed at the CASSCF level of theory, in which two electrons and two orbitals of the colliding hydrogen atoms are included in the active space. The trajectories were started by inserting the second hydrogen atom into the hydrogen atom-encapsulated-POSS (H + H@Tn → H2@Tn; n = 8 and 12). In many cases, the gradual formation of a hydrogen molecule has been observed after frequent collisions of two hydrogen atoms within the cages. The effect of the introduction of an argon atom in T12 is discussed as well.

Comments

Reprinted (adapted) with permission from Journal of Physical Chemistry A 115 (2011): 2679, doi:10.1021/jp1105778. Copyright 2011 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

Share

COinS