Actinyls in Expanded Porphyrin:  A Relativistic Density-Functional Study

Authors

M.-S. Liao
T. Kar
Steve Scheiner, Utah State UniversityFollow

Document Type

Article

Journal/Book Title

Journal of Physical Chemistry A

Publication Date

2004

Publisher

American Chemical Society

Volume

108

Issue

15

First Page

3056

Last Page

3063

Abstract

Actinyls AnO₂ with An = U, Np, and Pu in an expanded porphyrin, alaskaphyrin (AP), are studied by a relativistic density-functional method. The electronic structures of both AnO₂ and AnO₂AP are investigated by considering all possible low-lying states. To examine the importance of relativity, nonrelativistic calculations were also performed. For UO₂ and NpO₂, the ground state is altered by the relativistic effects, but it remains unchanged for PuO₂. The nonrelativistic ground states of the AnO₂AP complexes are all high spin, where the AP highest occupied molecular orbital, b_2g, is singly occupied. At the relativistic level, there are two electrons in b_2g. The bonding characteristics in AnO₂AP are examined by calculations of the AnO₂−AP binding energy and charge distribution on AnO₂. Other properties such as ionization potentials and electron affinities are also calculated. The predicted spectroscopic constants for NpO₂, PuO₂, NpO₂AP, and PuO₂AP would aid in future spectroscopic studies of these molecules.

Comments

Originally published by American Chemical Society in the Journal of Physical Chemistry.

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Recommended Citation

Actinyls in Expanded Porphyrin. A Relativistic Density Functional Study M.-S. Liao, T. Kar, S. Scheiner J. Phys. Chem. A 2004 108 3056-3063