Practical Intramolecular Symmetry Adapted Perturbation Theory via Hartree-Fock Embedding

We develop a simple methodology for the computation of symmetry-adapted perturbation theory (SAPT) interaction energy contributions for intramolecular noncovalent interactions. In this approach, the local occupied orbitals of the total Hartree-Fock (HF) wavefunction are used to partition the fully interacting system into three chemically identifiable units: the noncovalent fragments A and B and a covalent linker C. Once these units are identified, the noninteracting HF wavefunctions of the fragments A and B are separately optimized while embedded in the HF wavefunction of C, providing the dressed zeroth order wavefunctions for A and B in the presence of C. Standard two-body SAPT (particularly SAPT0) is then applied between the relaxed wavefunctions for A and B. This intramolecular SAPT procedure is found to be remarkably straightforward and efficient, as evidenced by example applications ranging from diols to hexaphenyl-ethane derivatives. (C) 2015 AIP Publishing LLC.


Published in:
Journal of Chemical Physics, 143, 5, 051103
Year:
2015
Publisher:
Melville, American Institute of Physics
ISSN:
0021-9606
Laboratories:




 Record created 2015-07-05, last modified 2018-03-17

External link:
Download fulltext
URL
Rate this document:

Rate this document:
1
2
3
 
(Not yet reviewed)