Interpolated potential energy surfaces: How accurate do the second derivatives have to be? (2005)

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Type of Content
Journal ArticlePublisher
AIP PublishingISSN
0021-96061089-7690
Language
engCollections
- Science: Journal Articles [1192]
Abstract
A global potential energy surface for the water dimer is constructed using the modified Shepard interpolation scheme of Collins et al. According to this interpolation scheme, the energy at an arbitrary geometry is expressed as a weighted sum of Taylor series expansions from neighboring data points, where the energy and derivative data required are obtained from ab initio calculations. For some ab initio methods, errors are introduced into the second derivative matrix, either by numerical differencing of ab initio energies or numerical integration during the ab initio calculation. Therefore, we test the accuracy required of the second derivative data by truncation of the exact second derivatives to a series of approximate second derivatives, and assess the effect on the results of a quantum diffusion Monte Carlo ~QDMC! simulation. Our results show that the calculated zero-point energy and wave function histograms converge to within the numerical uncertainty of the QDMC simulation by inclusion of either three significant figures or three decimal places in the second derivatives.
Citation
Crittenden DL, Jordan MJT (2005). Interpolated potential energy surfaces: How accurate do the second derivatives have to be?. The Journal of Chemical Physics. 122(4). 44102-.This citation is automatically generated and may be unreliable. Use as a guide only.
ANZSRC Fields of Research
34 - Chemical sciences::3407 - Theoretical and computational chemistry::340701 - Computational chemistry34 - Chemical sciences::3407 - Theoretical and computational chemistry::340704 - Theoretical quantum chemistry
34 - Chemical sciences::3406 - Physical chemistry::340607 - Reaction kinetics and dynamics
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