Assessment of various density functionals and basis sets for the calculation of molecular anharmonic force fields

2005/01/01 by A. Daniel Boese, Wim Klopper, Jan M. L. Martin · 71 citations
Chemistry · Mathematics · Physics and Astronomy · #Advanced Chemical Physics Studies #Anharmonicity #Basis (linear algebra) #Basis set #Chemical Thermodynamics and Molecular Structure #Density functional theory #Hybrid functional #Mathematics #Perturbation theory (quantum mechanics) #Physics #Quantum mechanics #Rigid rotor #Rotor (electric) #Spectroscopy and Quantum Chemical Studies #Statistical physics #physics.chem-ph #physics.comp-ph

paper · pdf · doi:10.1002/qua.20644

published in International Journal of Quantum Chemistry 104(5), 830-845 (Wiley) · Int. J. Quantum Chem., in press (special issue on vibrational spectroscopies)

openalex publication_date 2005/01/01 · arxiv created 2005/03/23 · arxiv updated 2009/12/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

Abstract In a previous contribution, we established the suitability of density functional theory (DFT) for the calculation of molecular anharmonic force fields. In the present work, we have assessed a wide variety of basis sets and exchange‐correlation functionals for harmonic and fundamental frequencies, equilibrium, and ground‐state rotational constants, and thermodynamic functions beyond the rigid rotor‐harmonic oscillator (RRHO) approximation. The fairly good performance of double‐zeta plus polarization basis sets for frequencies results from an error compensation between basis set incompleteness and the intrinsic error of exchange‐correlation functionals. Triple‐zeta plus polarization basis sets are recommended, with an additional high‐exponent d function on second‐row atoms. All conventional hybrid generalized gradient approximation (GGA) functionals perform about equally well: high‐exchange hybrid GGA and meta‐GGA functionals designed for kinetics yield poor results, with the exception of of the very recently developed BMK functional, which takes a middle position along with the HCTH/407 (second‐generation GGA) and TPSS (meta‐GGA) functionals. Second‐order Møller–Plesset perturbation theory (MP2) performs similarly to these functionals but is inferior to hybrid GGAs such as B3LYP and B97‐1. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005

Citations

• Generalized Gradient Approximation Made Simple
• Anharmonic force fields and thermodynamic functions using density functional theory
• Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
• Climbing the Density Functional Ladder: Nonempirical Meta–Generalized Gradient Approximation Designed for Molecules and Solids
• Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr
• Development of density functionals for thermochemical kinetics
• The role of the basis set: Assessing density functional theory
• Density-functional thermochemistry. III. The role of exact exchange

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