Characterization of the potential energy surfaces of two small but challenging noncovalent dimers: (P2)2 and (PCCP)2
Article first published online: 9 JAN 2014
Copyright © 2014 Wiley Periodicals, Inc.
Journal of Computational Chemistry
Volume 35, Issue 6, pages 479–487, 5 March 2014
How to Cite
How to cite this article: J. Comput. Chem. 2014, 35, 479–487. DOI:10.1002/jcc.23522, .
- Issue published online: 4 FEB 2014
- Article first published online: 9 JAN 2014
- Manuscript Accepted: 18 DEC 2013
- Manuscript Received: 13 DEC 2013
- National Science Foundation . Grant Numbers: CHE-0957317 , EPS-0903787
- noncovalent interactions;
- dispersion interactions;
- benchmark interaction energy;
- CCSD(T) complete basis set limit;
- symmetry-adapted perturbation theory
This work characterizes eight stationary points of the P2 dimer and six stationary points of the PCCP dimer, including a newly identified minimum on both potential energy surfaces. Full geometry optimizations and corresponding harmonic vibrational frequencies were computed with the second-order Møller–Plesset (MP2) electronic structure method and six different basis sets: aug-cc-pVXZ, aug-cc-pV(X+d)Z, and aug-cc-pCVXZ where X = T, Q. A new L-shaped structure with C2 symmetry is the only minimum for the P2 dimer at the MP2 level of theory with these basis sets. The previously reported parallel-slipped structure with C2h symmetry and a newly identified cross configuration with D2 symmetry are the only minima for the PCCP dimer. Single point energies were also computed using the canonical MP2 and CCSD(T) methods as well as the explicitly correlated MP2-F12 and CCSD(T)-F12 methods and the aug-cc-pVXZ (X = D, T, Q, 5) basis sets. The energetics obtained with the explicitly correlated methods were very similar to the canonical results for the larger basis sets. Extrapolations were performed to estimate the complete basis set (CBS) limit MP2 and CCSD(T) binding energies. MP2 and MP2-F12 significantly overbind the P2 and PCCP dimers relative to the CCSD(T) and CCSD(T)-F12 binding energies by as much as 1.5 kcal mol−1 for the former and 5.0 kcal mol−1 for the latter at the CBS limit. The dominant attractive component of the interaction energy for each dimer configuration was dispersion according to several symmetry-adapted perturbation theory analyses. © 2014 Wiley Periodicals, Inc.