Accelerating self-consistent field convergence with the augmented Roothaan–Hall energy function

Hu, Xiangqian; Yang, Weitao

doi:doi:10.1063/1.3304922

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Correlation consistent basis sets for molecular core-valence effects with explicitly correlated wave functions: The atoms B–Ne and Al–Ar

Correlation consistent basis sets have been optimized for accurately describing core-core and core-valence correlation effects with explicitly correlated F12 methods. The new sets, denoted cc-pCVnZ-F12 (n = D, T, Q) and aug-cc-pCF12VnZ (n = D, T, Q, 5), were developed by augmenting the cc-pVnZ-F12 and aug-cc-pVnZ families of basis sets with additional functions whose exponents were optimized based on the difference between all-electron and valence-electron correlation energies. The number of au...

B3LYP calculations of cerium oxides

In this paper we evaluate the performance of density functional theory with the B3LYP functional for calculations on ceria (CeO2) and cerium sesquioxide (Ce2O3). We demonstrate that B3LYP is able to describe CeO2 and Ce2O3 reasonably well. When compared to other functionals, B3LYP performs slightly better than the hybrid functional PBE0 for the electronic properties but slightly worse for the structural properties, although neither performs as well as LDA+U(U = 6 eV) or PBE+U(U = 5 eV). We also...

Based on Pulay’s direct inversion iterative subspace (DIIS) approach, we present a method to accelerate self-consistent field (SCF) convergence. In this method, the quadratic augmented Roothaan–Hall (ARH) energy function, proposed recently by Høst and co-workers [J. Chem. Phys. 129, 124106 (2008)] , is used as the object of minimization for obtaining the linear coefficients of Fock matrices within DIIS. This differs from the traditional DIIS of Pulay, which uses an object function derived from the commutator of the density and Fock matrices. Our results show that the present algorithm, abbreviated ADIIS, is more robust and efficient than the energy-DIIS (EDIIS) approach. In particular, several examples demonstrate that the combination of ADIIS and DIIS (“ADIIS+DIIS”) is highly reliable and efficient in accelerating SCF convergence.

Article Outline

INTRODUCTION
METHODS
1. The ARH energy function
2. The ADIIS algorithm
RESULTS
1. Well-behaved molecular systems: CH₃CHO and a water cluster
2. A challenging system: A cadmium complex
3. A typical biological system: A polyalanine peptide
4. Problem cases: Two Ruthenium compounds
CONCLUSIONS

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KEYWORDS and PACS

Keywords

convergence of numerical methods, SCF calculations

PACS

31.15.xr

Self-consistent-field methods

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http://dx.doi.org/10.1063/1.3304922

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0021-9606 (print)

1089-7690 (online)

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$abstract.society.value is a Member of CrossRef

American Institute of Physics

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