Communication: Practical intramolecular symmetry adapted perturbation theory via Hartree-Fock embedding

Robert M Parrish; Jérôme F Gonthier; Clémence Corminbœuf; C David Sherrill

doi:10.1063/1.4927575

Communication: Practical intramolecular symmetry adapted perturbation theory via Hartree-Fock embedding

J Chem Phys. 2015 Aug 7;143(5):051103. doi: 10.1063/1.4927575.

Authors

Robert M Parrish¹, Jérôme F Gonthier¹, Clémence Corminbœuf², C David Sherrill¹

Affiliations

¹ Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, School of Computational Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
² Laboratory for Computational Molecular Design, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland.

PMID: 26254634
DOI: 10.1063/1.4927575

Abstract

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.