Actinide chemistry using singlet-paired coupled cluster and its combinations with density functionals.

J Chem Phys

Department of Chemistry and Department of Physics and Astronomy, Rice University, Houston, Texas 77251-1892, USA.

Published: December 2015

Singlet-paired coupled cluster doubles (CCD0) is a simplification of CCD that relinquishes a fraction of dynamic correlation in order to be able to describe static correlation. Combinations of CCD0 with density functionals that recover specifically the dynamic correlation missing in the former have also been developed recently. Here, we assess the accuracy of CCD0 and CCD0+DFT (and variants of these using Brueckner orbitals) as compared to well-established quantum chemical methods for describing ground-state properties of singlet actinide molecules. The f(0) actinyl series (UO2(2+), NpO2(3+), PuO2(4+)), the isoelectronic NUN, and thorium (ThO, ThO(2+)) and nobelium (NoO, NoO2) oxides are studied.

Download full-text PDF

Source
http://dx.doi.org/10.1063/1.4938088DOI Listing

Publication Analysis

Top Keywords

singlet-paired coupled
8
coupled cluster
8
density functionals
8
dynamic correlation
8
actinide chemistry
4
chemistry singlet-paired
4
cluster combinations
4
combinations density
4
functionals singlet-paired
4
cluster doubles
4

Similar Publications

It is well known that single-reference coupled cluster theory truncated to low orders of excitations gives the right answer for the right reason when systems are dominated by dynamical or weak correlation. Static or strong correlation is more problematic, causing often catastrophic breakdown of restricted coupled cluster. This failure can be remedied, e.

View Article and Find Full Text PDF

Singlet-paired coupled cluster theory for open shells.

J Chem Phys

June 2016

Department of Chemistry, Rice University, Houston, Texas 77005, USA.

Restricted single-reference coupled cluster theory truncated to single and double excitations accurately describes weakly correlated systems, but often breaks down in the presence of static or strong correlation. Good coupled cluster energies in the presence of degeneracies can be obtained by using a symmetry-broken reference, such as unrestricted Hartree-Fock, but at the cost of good quantum numbers. A large body of work has shown that modifying the coupled cluster ansatz allows for the treatment of strong correlation within a single-reference, symmetry-adapted framework.

View Article and Find Full Text PDF

Actinide chemistry using singlet-paired coupled cluster and its combinations with density functionals.

J Chem Phys

December 2015

Department of Chemistry and Department of Physics and Astronomy, Rice University, Houston, Texas 77251-1892, USA.

Singlet-paired coupled cluster doubles (CCD0) is a simplification of CCD that relinquishes a fraction of dynamic correlation in order to be able to describe static correlation. Combinations of CCD0 with density functionals that recover specifically the dynamic correlation missing in the former have also been developed recently. Here, we assess the accuracy of CCD0 and CCD0+DFT (and variants of these using Brueckner orbitals) as compared to well-established quantum chemical methods for describing ground-state properties of singlet actinide molecules.

View Article and Find Full Text PDF

Can Single-Reference Coupled Cluster Theory Describe Static Correlation?

J Chem Theory Comput

July 2015

Department of Chemistry, Rice University, Houston, Texas 77005-1892, United States.

While restricted single-reference coupled cluster theory truncated to singles and doubles (CCSD) provides very accurate results for weakly correlated systems, it usually fails in the presence of static or strong correlation. This failure is generally attributed to the qualitative breakdown of the reference, and can accordingly be corrected by using a multideterminant reference, including higher-body cluster operators in the ansatz, or allowing symmetry breaking in the reference. None of these solutions are ideal; multireference coupled cluster is not black box, including higher-body cluster operators is computationally demanding, and allowing symmetry breaking leads to the loss of good quantum numbers.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!