Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

10-2002

Journal or Book Title

Journal of Physical Chemistry A

Volume

106

Issue

45

First Page

11764

Last Page

11770

DOI

10.1021/jp021490f

Abstract

The process of insertion of molecular oxygen and nitrogen into polyhedral oligomeric silsesquioxanes (POSS) has been investigated theoretically. Using ab initio methods, the N2interaction with the POSS has been described with restricted Hartree−Fock (RHF) with a triple-ζ basis set, while systems involving O2 require restricted open shell (ROHF) wave functions, to account for their open-shell ground states. This insertion process is described in terms of the energetic change that the system X2::POSS undergoes when the gas molecule passes from the exterior to the interior of the cage through the largest of its faces. The formation of the cluster occurs through a transition structure that has been characterized for each system. The barrier is a function of the dimension of the face of the POSS and, hence, of the cage dimensions. The results of the calculation are consistent with experimental observations that the O2 molecules pass through a given membrane more easily than N2.

Comments

Reprinted (adapted) with permission from Journal of Physical Chemistry A 106 (2002): 11764, doi:10.1021/jp021490f. Copyright 2002 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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