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Title: Atomic Orbital Implementation of Extended Symmetry-Adapted Perturbation Theory (XSAPT) and Benchmark Calculations for Large Supramolecular Complexes

Journal Article · · Journal of Chemical Theory and Computation
 [1]; ORCiD logo [1]
  1. The Ohio State Univ., Columbus, OH (United States)
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We report an implementation of extended symmetry-adapted perturbation theory (XSAPT) in the atomic orbital basis, extending this method to systems where the monomers are large. In our “XSAPT(KS)” approach, monomers are described using range-separated Kohn–Sham (KS) density functional theory (DFT), with correct asymptotic behavior set by tuning the range-separation parameter ω in a monomer-specific way. This is accomplished either by conventional ionization potential (IP)-based tuning, in which ω is adjusted to satisfy the condition εHOMO(ω) = -IP(ω), or else using a “global density-dependent” (GDD) condition, in which ω is fixed based on the size of the exchange hole. The latter procedure affords better results for both total interaction energies and energy components, when used in conjunction with our third-generation pairwise atom–atom dispersion potential (+aiD3). Three-body (triatomic) dispersion terms are found to be important when the monomers are large, and we incorporate these by means of an Axilrod–Teller–Muto term, Edisp,3BATM, which reduces errors in supramolecular interaction energies by about a factor of 2. The XSAPT(KS) + aiD3 + Edisp,3BATM(ωGDD) approach affords mean absolute errors as low as 1.2 and 4.2 kcal/mol, respectively, for the L7 and S12L benchmark test sets of large dimers. Such errors are comparable to those afforded by far more expensive methods, such as DFT-SAPT, and the closely related second-order perturbation theory with coupled dispersion (MP2C). We also survey the performance of various other quantum-chemical methods for these data sets and identify several semiempirical and DFT-based approaches whose accuracy approaches that of MP2C, at dramatically reduced cost.

Research Organization:
The Ohio State Univ., Columbus, OH (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0008850
OSTI ID:
1604462
Journal Information:
Journal of Chemical Theory and Computation, Vol. 14, Issue 6; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 42 works
Citation information provided by
Web of Science

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