Literature DB >> 21428611

The two faces of static correlation.

Joshua W Hollett1, Peter M W Gill.   

Abstract

Restricted Hartree-Fock (RHF) and UHF wavefunctions for beryllium-like ions with nuclear charge 3 ≤ Z ≤ 5 are found using a near-complete Slater basis set. The triplet (RHF → UHF) instability and correlation energy are investigated as a function of Z and we find that the instability vanishes for Z > 4.5. We reproduce this surprising behavior using a minimal-basis model and, by comparing with the stretched H(2) molecule, conclude that "static" (also known as nondynamical, near-degeneracy, first-order, or strong) correlation comes in two flavors: one that can be captured by UHF and another that cannot. In the former (Type A), there is an "absolute near-degeneracy"; in the latter (Type B), there is a "relative near-degeneracy." This dichotomy clarifies discussions of static correlation effects.

Entities:  

Year:  2011        PMID: 21428611     DOI: 10.1063/1.3570574

Source DB:  PubMed          Journal:  J Chem Phys        ISSN: 0021-9606            Impact factor:   3.488


  7 in total

1.  Improved self-consistent and resolution-of-identity approximated Becke'05 density functional model of nondynamic electron correlation.

Authors:  Emil Proynov; Fenglai Liu; Yihan Shao; Jing Kong
Journal:  J Chem Phys       Date:  2012-01-21       Impact factor: 3.488

2.  Do Double-Hybrid Functionals Benefit from Regularization in the PT2 Term? Observations from an Extensive Benchmark.

Authors:  Golokesh Santra; Jan M L Martin
Journal:  J Phys Chem Lett       Date:  2022-04-13       Impact factor: 6.475

3.  Density matrix renormalization group pair-density functional theory (DMRG-PDFT): singlet-triplet gaps in polyacenes and polyacetylenes.

Authors:  Prachi Sharma; Varinia Bernales; Stefan Knecht; Donald G Truhlar; Laura Gagliardi
Journal:  Chem Sci       Date:  2018-11-26       Impact factor: 9.825

4.  Active Learning Configuration Interaction for Excited-State Calculations of Polycyclic Aromatic Hydrocarbons.

Authors:  WooSeok Jeong; Carlo Alberto Gaggioli; Laura Gagliardi
Journal:  J Chem Theory Comput       Date:  2021-11-17       Impact factor: 6.006

5.  Performance of Localized Coupled Cluster Methods in a Moderately Strong Correlation Regime: Hückel-Möbius Interconversions in Expanded Porphyrins.

Authors:  Nitai Sylvetsky; Ambar Banerjee; Mercedes Alonso; Jan M L Martin
Journal:  J Chem Theory Comput       Date:  2020-05-11       Impact factor: 6.006

6.  Canonical and DLPNO-Based Composite Wavefunction Methods Parametrized against Large and Chemically Diverse Training Sets. 2: Correlation-Consistent Basis Sets, Core-Valence Correlation, and F12 Alternatives.

Authors:  Emmanouil Semidalas; Jan M L Martin
Journal:  J Chem Theory Comput       Date:  2020-11-17       Impact factor: 6.006

7.  The MOBH35 Metal-Organic Barrier Heights Reconsidered: Performance of Local-Orbital Coupled Cluster Approaches in Different Static Correlation Regimes.

Authors:  Emmanouil Semidalas; Jan M L Martin
Journal:  J Chem Theory Comput       Date:  2022-01-19       Impact factor: 6.006

  7 in total

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