Literature DB >> 23452230

What can we learn about dispersion from the conformer surface of n-pentane?

Jan M L Martin1.   

Abstract

In earlier work [Gruzman, D. ; Karton, A.; Martin, J. M. L. J. Phys. Chem. A 2009, 113, 11974], we showed that conformer energies in alkanes (and other systems) are highly dispersion-driven and that uncorrected DFT functionals fail badly at reproducing them, while simple empirical dispersion corrections tend to overcorrect. To gain greater insight into the nature of the phenomenon, we have mapped the torsional surface of n-pentane to 10-degree resolution at the CCSD(T)-F12 level near the basis set limit. The data obtained have been decomposed by order of perturbation theory, excitation level, and same-spin vs opposite-spin character. A large number of approximate electronic structure methods have been considered, as well as several empirical dispersion corrections. Our chief conclusions are as follows: (a) the effect of dispersion is dominated by same-spin correlation (or triplet-pair correlation, from a different perspective); (b) singlet-pair correlation is important for the surface, but qualitatively very dissimilar to the dispersion component; (c) single and double excitations beyond third order are essentially unimportant for this surface; (d) connected triple excitations do play a role but are statistically very similar to the MP2 singlet-pair correlation; (e) the form of the damping function is crucial for good performance of empirical dispersion corrections; (f) at least in the lower-energy regions, SCS-MP2 and especially MP2.5 perform very well; (g) novel spin-component scaled double hybrid functionals such as DSD-PBEP86-D2 acquit themselves very well for this problem.

Entities:  

Year:  2013        PMID: 23452230     DOI: 10.1021/jp401429u

Source DB:  PubMed          Journal:  J Phys Chem A        ISSN: 1089-5639            Impact factor:   2.781


  5 in total

1.  A DFT study on the thermal cracking of JP-10.

Authors:  Lei Yue; Hu-Jun Xie; Xiao-Mei Qin; Xiao-Xing Lu; Wen-Jun Fang
Journal:  J Mol Model       Date:  2013-10-27       Impact factor: 1.810

2.  Fast, accurate evaluation of exact exchange: The occ-RI-K algorithm.

Authors:  Samuel Manzer; Paul R Horn; Narbe Mardirossian; Martin Head-Gordon
Journal:  J Chem Phys       Date:  2015-07-14       Impact factor: 3.488

3.  Survival of the most transferable at the top of Jacob's ladder: Defining and testing the ωB97M(2) double hybrid density functional.

Authors:  Narbe Mardirossian; Martin Head-Gordon
Journal:  J Chem Phys       Date:  2018-06-28       Impact factor: 3.488

4.  Unraveling the performance of dispersion-corrected functionals for the accurate description of weakly bound natural polyphenols.

Authors:  Florent Di Meo; Imene Bayach; Patrick Trouillas; Juan-Carlos Sancho-García
Journal:  J Mol Model       Date:  2015-10-26       Impact factor: 1.810

5.  Minimally Empirical Double-Hybrid Functionals Trained against the GMTKN55 Database: revDSD-PBEP86-D4, revDOD-PBE-D4, and DOD-SCAN-D4.

Authors:  Golokesh Santra; Nitai Sylvetsky; Jan M L Martin
Journal:  J Phys Chem A       Date:  2019-06-12       Impact factor: 2.944

  5 in total

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