A RASSCF study of free base, magnesium and zinc porphyrins:accuracy versus efficiency

Kerridge, Andrew (2013) A RASSCF study of free base, magnesium and zinc porphyrins:accuracy versus efficiency. Physical Chemistry Chemical Physics, 15 (6). pp. 2197-2209. ISSN 1463-9076

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Abstract

The restricted-active-space self-consistent-field methodology is successfully applied to the study of free base-and regular metalloporphyrins, the latter containing magnesium and zinc central ions. It is shown that inclusion of all excitations involving the Gouterman frontier orbitals in the RAS2 subspace results in a numerically stable approach, producing highly accurate results at a fraction of the computational cost of the complete-active-space self-consistent-field method, whereas increasing RAS2 beyond this size leads to only modest improvement. Topological and orbital analysis shows that the approach is also able to give a highly accurate description of the electronic wavefunction. Inclusion of the entire p-conjugated subsystem in the active space results in more accurate excitation energies and a reduction in the dependence on the exact form of the perturbational Hamiltonian used to include dynamic correlation. The larger active space also resolves a quantitative disagreement in results obtained with and without the inclusion of dynamic correlation.

Item Type:
Journal Article
Journal or Publication Title:
Physical Chemistry Chemical Physics
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/1600/1606
Subjects:
ID Code:
71570
Deposited By:
Deposited On:
03 Nov 2014 14:13
Refereed?:
Yes
Published?:
Published
Last Modified:
01 Apr 2020 03:45