Document Detail

Comparison of some dispersion-corrected and traditional functionals with CCSD(T) and MP2 ab initio methods: dispersion, induction, and basis set superposition error.
MedLine Citation:
PMID:  23039587     Owner:  NLM     Status:  MEDLINE    
We compare dispersion and induction interactions for noble gas dimers and for Ne, methane, and 2-butyne with HF and LiF using a variety of functionals (including some specifically parameterized to evaluate dispersion interactions) with ab initio methods including CCSD(T) and MP2. We see that inductive interactions tend to enhance dispersion and may be accompanied by charge-transfer. We show that the functionals do not generally follow the expected trends in interaction energies, basis set superposition errors (BSSE), and interaction distances as a function of basis set size. The functionals parameterized to treat dispersion interactions often overestimate these interactions, sometimes by quite a lot, when compared to higher level calculations. Which functionals work best depends upon the examples chosen. The B3LYP and X3LYP functionals, which do not describe pure dispersion interactions, appear to describe dispersion mixed with induction about as accurately as those parametrized to treat dispersion. We observed significant differences in high-level wavefunction calculations in a basis set larger than those used to generate the structures in many of the databases. We discuss the implications for highly parameterized functionals based on these databases, as well as the use of simple potential energy for fitting the parameters rather than experimentally determinable thermodynamic state functions that involve consideration of vibrational states.
Dipankar Roy; Mateusz Marianski; Neepa T Maitra; J J Dannenberg
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Publication Detail:
Type:  Comparative Study; Journal Article; Research Support, N.I.H., Extramural; Research Support, U.S. Gov't, Non-P.H.S.    
Journal Detail:
Title:  The Journal of chemical physics     Volume:  137     ISSN:  1089-7690     ISO Abbreviation:  J Chem Phys     Publication Date:  2012 Oct 
Date Detail:
Created Date:  2012-10-08     Completed Date:  2013-02-20     Revised Date:  2013-10-17    
Medline Journal Info:
Nlm Unique ID:  0375360     Medline TA:  J Chem Phys     Country:  United States    
Other Details:
Languages:  eng     Pagination:  134109     Citation Subset:  IM    
Departments of Chemistry, City University of New York-Hunter College and the Graduate School, 695 Park Avenue, New York, New York 10065, USA.
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MeSH Terms
Alkynes / chemistry
Fluorides / chemistry
Hydrofluoric Acid / chemistry
Lithium Compounds / chemistry
Methane / chemistry
Noble Gases / chemistry
Quantum Theory*
Grant Support
Reg. No./Substance:
0/Alkynes; 0/Fluorides; 0/Lithium Compounds; 0/Noble Gases; 1485XST65B/lithium fluoride; 74-82-8/Methane; 7664-39-3/Hydrofluoric Acid

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