Density-fitted open-shell symmetry-adapted perturbation theory and application to π-stacking in benzene dimer cation and ionized DNA base pair steps

Symmetry-Adapted Perturbation Theory (SAPT) is one of the most popular approaches to energy component analysis of non-covalent interactions between closed-shell systems, yielding both accurate interaction energies and meaningful interaction energy components. In recent years, the full open-shell equ...

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Bibliographic Details
Published in:The Journal of chemical physics 2016-10, Vol.145 (13), p.134106-134106
Main Authors: Gonthier, Jérôme F., Sherrill, C. David
Format: Article
Language:English
Subjects:
Base Pairing
Benzene
Benzene - chemistry
Cations
Cations - chemistry
Charge transfer
Density
Deoxyribonucleic acid
Dimerization
Dimers
DNA
DNA - chemistry
Hydrocarbons
Hydrogen Bonding
Hydrogen storage
Ionization
Ions - chemistry
Models, Chemical
Perturbation theory
Quantum Theory
Stacking
Symmetry
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Summary:Symmetry-Adapted Perturbation Theory (SAPT) is one of the most popular approaches to energy component analysis of non-covalent interactions between closed-shell systems, yielding both accurate interaction energies and meaningful interaction energy components. In recent years, the full open-shell equations for SAPT up to second-order in the intermolecular interaction and zeroth-order in the intramolecular correlation (SAPT0) were published [P. S. Zuchowski et al., J. Chem. Phys. 129, 084101 (2008); M. Hapka et al., ibid. 137, 164104 (2012)]. Here, we utilize density-fitted electron repulsion integrals to produce an efficient computational implementation. This approach is used to examine the effect of ionization on π-π interactions. For the benzene dimer radical cation, comparison against reference values indicates a good performance for open-shell SAPT0, except in cases with substantial charge transfer. For π stacking between hydrogen-bonded pairs of nucleobases, dispersion interactions still dominate binding, in spite of the creation of a positive charge.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4963385