Accuracy of Dispersion Interactions in Semiempirical and Molecular Mechanics Models: The Benzene Dimer Case
authors Strutynski, K; Gomes, JANF; Melle-Franco, M
journal JOURNAL OF PHYSICAL CHEMISTRY A
keywords DENSITY-FUNCTIONAL-THEORY; POTENTIAL-ENERGY SURFACE; MM3 FORCE-FIELD; CARBON NANOTUBES; NDDO APPROXIMATIONS; GROUND-STATES; DFT-D; DYNAMICS; OPTIMIZATION; PARAMETERS
abstract The benzene dimer is arguably the simplest molecular analogue of graphitic materials. We present the systematic study of minima and transition states of the benzene dimer with semiempirical and molecular mechanics (MM) methods. Full minimizations on all conformations were performed and the results, geometries, and binding energies were compared with CCSD(T) and DFT-D results. MM yields the best results with three force fields MM3, OPLS, and AMOEBA, which reproduced nine out of the ten stationary points of the benzene dimer. We obtained new parameters for MM3 and OPLS that successfully reproduce all structures of the benzene dimer and showed improved accuracy over DFT-D in most dimer geometries. Semiempirical models were, unexpectedly, less accurate than MM methods. The most accurate semiempirical method for the benzene dimer is PM6-DH2. DFT-D was the only Hamiltonian that reproduced the variations of energy with geometry from CCSD(T) calculations accurately and is the method of choice for energies of periodic and molecular calculations of graphitic systems. In contrast, MM represents an accurate alternative to calculate geometries.
publisher AMER CHEMICAL SOC
issn 1089-5639
year published 2014
volume 118
issue 40
beginning page 9561
ending page 9567
digital object identifier (doi) 10.1021/jp506860t
web of science category Chemistry, Physical; Physics, Atomic, Molecular & Chemical
subject category Chemistry; Physics
unique article identifier WOS:000343016900029
  ciceco authors
  impact metrics
times cited (wos core): 8
journal impact factor (jcr 2016): 2.847
5 year journal impact factor (jcr 2016): 2.663
category normalized journal impact factor percentile (jcr 2016): 61.970
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