Title:
Hybrid Correlation Models For Bond Breaking Based On Active Space Partitioning
Hybrid Correlation Models For Bond Breaking Based On Active Space Partitioning
Author(s)
Bochevarov, Artem D.
Advisor(s)
Sherrill, C. David
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Abstract
The work presented in this thesis is dedicated to developing inexpensive quantum-chemical models that are able to produce smooth and physically correct potential energy curves for the
dissociation of single covalent bonds. It is well known that the energies produced by many ab initio theories scaling as the fifth order with the system size (for instance, second-order
Moller-Plesset (MP2) and Epstein-Nesbet perturbation theories) diverge at large interatomic separations. We show that the
divergent behavior of such perturbation schemes is due to a small number of terms in the energy expressions. Then, we demonstrate that the self-consistent replacement of these terms by their
analogs from the coupled cluster theory (such as CCSD) allows one to redress the erroneous behavior of the perturbation theories
without the damage to the overall scaling.
We also investigate the accuracy of these hybrid perturbation theory-coupled cluster theories near equilibrium geometry. Judging from the computed spectroscopic constants and shapes of the potential energy curves, one such model, denoted
MP2-CCSD(II) in this work, performs consistently better than the MP2 theory at essentially the same computational cost.
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Date Issued
2006-07-10
Extent
2076351 bytes
Resource Type
Text
Resource Subtype
Dissertation