We introduce an intramolecular energy decomposition scheme for analyzing non-covalent interactions within molecules in the spirit of symmetry-adapted perturbation theory (SAPT). The proposed intra-SAPT approach is based upon the Chemical Hamiltonian of Mayer [Int. J. Quantum Chem. 23(2), 341–363 (1983)] and the recently introduced zeroth-order wavefunction [J. F. Gonthier and C. Corminboeuf, J. Chem. Phys. 140(15), 154107 (2014)]. The scheme decomposes the interaction energy between weakly bound fragments located within the same molecule into physically meaningful components, i.e., electrostatic-exchange, induction, and dispersion. Here, we discuss the key steps of the approach and demonstrate that a single-determinant wavefunction can already deliver a detailed and insightful description of a wide range of intramolecular non-covalent phenomena such as hydrogen bonds, dihydrogen contacts, and π − π stacking interactions. Intra-SAPT is also used to shed the light on competing intra- and intermolecular interactions.
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14 December 2015
Research Article|
December 09 2015
Intramolecular symmetry-adapted perturbation theory with a single-determinant wavefunction
Ewa Pastorczak;
Ewa Pastorczak
a)
1Laboratory for Computational Molecular Design, Institut des Sciences et Ingénierie Chimiques,
École Polytechnique Fédérale de Lausanne
, CH-1015 Lausanne, Switzerland
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Antonio Prlj;
Antonio Prlj
a)
1Laboratory for Computational Molecular Design, Institut des Sciences et Ingénierie Chimiques,
École Polytechnique Fédérale de Lausanne
, CH-1015 Lausanne, Switzerland
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Jérôme F. Gonthier
;
Jérôme F. Gonthier
2Center 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
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Clémence Corminboeuf
Clémence Corminboeuf
b)
1Laboratory for Computational Molecular Design, Institut des Sciences et Ingénierie Chimiques,
École Polytechnique Fédérale de Lausanne
, CH-1015 Lausanne, Switzerland
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a)
E. Pastorczak and A. Prlj contributed equally to this work.
b)
Electronic mail: clemence.corminboeuf@epfl.ch
J. Chem. Phys. 143, 224107 (2015)
Article history
Received:
September 14 2015
Accepted:
November 18 2015
Citation
Ewa Pastorczak, Antonio Prlj, Jérôme F. Gonthier, Clémence Corminboeuf; Intramolecular symmetry-adapted perturbation theory with a single-determinant wavefunction. J. Chem. Phys. 14 December 2015; 143 (22): 224107. https://doi.org/10.1063/1.4936830
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