dorsal/arxiv
View SchemaAnharmonic force fields and thermodynamic functions using density functional theory
| Authors | A. Daniel Boese, Wim Klopper, Jan M. L. Martin |
|---|---|
| Categories | |
| ArXiv ID | physics/0411065 |
| URL | https://arxiv.org/abs/physics/0411065 |
| DOI | 10.1080/00268970512331339369 |
| Journal | Molecular Physics 103, 863-876 (2005) |
Abstract
The very good performance of modern density functional theory for molecular geometries and harmonic vibrational frequencies has been well established. We investigate the performance of density functional theory (DFT) for quartic force fields, vibrational anharmonicity and rotation-vibration coupling constants, and thermodynamic functions beyond the RRHO (rigid rotor-harmonic oscillator) approximation of a number of small polyatomic molecules. Convergence in terms of basis set, integration grid and the numerical step size for determining the quartic force field by using central differences of analytical second derivatives has been investigated, as well as the performance of various exchange-correlation functionals. DFT is found to offer a cost-effective approach with manageable scalability for obtaining anharmonic molecular properties, and particularly as a source for anharmonic zero-point and thermal corrections for use in conjunction with benchmark {\it ab initio} thermochemistry methods.
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"abstract": "The very good performance of modern density functional theory for molecular\ngeometries and harmonic vibrational frequencies has been well established. We\ninvestigate the performance of density functional theory (DFT) for quartic\nforce fields, vibrational anharmonicity and rotation-vibration coupling\nconstants, and thermodynamic functions beyond the RRHO (rigid rotor-harmonic\noscillator) approximation of a number of small polyatomic molecules.\nConvergence in terms of basis set, integration grid and the numerical step size\nfor determining the quartic force field by using central differences of\nanalytical second derivatives has been investigated, as well as the performance\nof various exchange-correlation functionals. DFT is found to offer a\ncost-effective approach with manageable scalability for obtaining anharmonic\nmolecular properties, and particularly as a source for anharmonic zero-point\nand thermal corrections for use in conjunction with benchmark {\\it ab initio}\nthermochemistry methods.",
"arxiv_id": "physics/0411065",
"authors": [
"A. Daniel Boese",
"Wim Klopper",
"Jan M. L. Martin"
],
"categories": [
"physics.chem-ph",
"physics.comp-ph"
],
"doi": "10.1080/00268970512331339369",
"journal_ref": "Molecular Physics 103, 863-876 (2005)",
"title": "Anharmonic force fields and thermodynamic functions using density functional theory",
"url": "https://arxiv.org/abs/physics/0411065"
},
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