Dispersion-Corrected Density Functional Theory Calculations of meso-Tetraphenylporphine-C-60 Complex by Using DMol3 Module

作者：Basiuk Vladimir A^*; Veronica Henao Holguin Laura

来源：Journal of Computational and Theoretical Nanoscience, 2014, 11(7): 1609-1615.

DOI：10.1166/jctn.2014.3539

• Density Functional Theory
• DMol3 Module
• Porphyrin
• Fullerene C-60
• Dispersion Correction

We performed a series of DMol3 calculations of geometry, energy and some electronic properties of the noncovalent dyad of meso-tetraphenylporphine and fullerene C-60 (H2TPP-C-60) by applying different types of dispersion correction (as well as without it, for comparison), in order to suggest a computational methodology capable of yielding most realistic results in theoretical studies of the interactions of porphyrin-like compounds with carbon nanoclusters. The method evaluation was based on the binding energies Delta E and the shortest intermolecular contacts N-H2TPP center dot center dot center dot C-C60. The binding energy values closely matching the best estimates reported elsewhere were -25.5 and -25.2 kcal/mol calculated with PBE GGA functional and Grimme dispersion correction, in conjunction with DNP basis set versions 3.5 and 4.4, respectively. TS-corrected PBE calculations yielded weaker binding (-19.5 and -16.1 kcal/mol for the basis set versions 3.5 and 4.4, respectively), whereas OBS-corrected PW91 functional predicted much stronger association (-43.1 and -42.6 kcal/mol, respectively). The values for closest contacts N-H2TPP center dot center dot center dot C-C60, which are systematically overestimated by pure GGA functionals, were dramatically improved by applying Grimme or TS dispersion correction to PBE, and OBS correction to PW91 functional. All the resulting calculated N-H2TPP center dot center dot center dot C-C60 separations matched very well the corresponding experimental distances of about 3.0 angstrom, where the best results were obtained with Grimme-corrected PBE and OBS-corrected PW91. Based on the above, of GGA and LDA functionals available in DMol3 module, PBE functional along with Grimme dispersion correction can be suggested as the computational methodology most suitable for theoretical studies of the interactions of porphyrin-like compounds with larger carbon nanoclusters such as carbon nanotubes and graphene.

• 出版日期2014-7