Breakdown of the single-exchange approximation in third-order symmetry-adapted perturbation theory

The Journal of Physical Chemistry. a
Ka Un Lao, John M Herbert

Abstract

We report third-order symmetry-adapted perturbation theory (SAPT) calculations for several dimers whose intermolecular interactions are dominated by induction. We demonstrate that the single-exchange approximation (SEA) employed to derive the third-order exchange-induction correction (E(exch-ind)((30))) fails to quench the attractive nature of the third-order induction (E(ind)((30))), leading to one-dimensional potential curves that become attractive rather than repulsive at short intermolecular separations. A scaling equation for (E(exch-ind)((30))), based on an exact formula for the first-order exchange correction, is introduced to approximate exchange effects beyond the SEA, and qualitatively correct potential energy curves that include third-order induction are thereby obtained. For induction-dominated systems, our results indicate that a "hybrid" SAPT approach, in which a dimer Hartree-Fock calculation is performed in order to obtain a correction for higher-order induction, is necessary not only to obtain quantitative binding energies but also to obtain qualitatively correct potential energy surfaces. These results underscore the need to develop higher-order exchange-induction formulas that go beyond the SEA.

References

Aug 25, 2006·The Journal of Physical Chemistry. a·Rafał PodeszwaKrzysztof Szalewicz
Oct 25, 2006·The Journal of Chemical Physics·Konrad PatkowskiBogumił Jeziorski
Oct 25, 2007·Physical Chemistry Chemical Physics : PCCP·Rafał PodeszwaKrzysztof Szalewicz
Oct 15, 2008·Physical Review Letters·Rafał PodeszwaKrzysztof Szalewicz
Jun 25, 2009·Physical Chemistry Chemical Physics : PCCP·Rafal PodeszwaKrzysztof Szalewicz
Jul 9, 2011·The Journal of Physical Chemistry. B·Kuang YuJ R Schmidt
Sep 13, 2011·Journal of Chemical Theory and Computation·Edward G HohensteinC David Sherrill

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Citations

Mar 13, 2014·The Journal of Chemical Physics·Trent M ParkerC David Sherrill
Dec 18, 2013·The Journal of Chemical Physics·Ryan M RichardJohn M Herbert
Jan 8, 2016·Physical Chemistry Chemical Physics : PCCP·Yu-Ting ChenJeng-Da Chai
Apr 8, 2017·The Journal of Chemical Physics·Ewa Pastorczak, Clémence Corminboeuf
May 18, 2020·The Journal of Chemical Physics·Javier GarciaKrzysztof Szalewicz
Jan 16, 2021·The Journal of Chemical Physics·Jonathan M Waldrop, Konrad Patkowski
Apr 3, 2021·The Journal of Physical Chemistry. B·Xiaoyang LiuC Heath Turner
Aug 8, 2012·The Journal of Physical Chemistry. a·Piotr Matczak
Mar 12, 2013·Journal of Chemical Theory and Computation·Ryan M Richard, John M Herbert
Oct 2, 2012·Accounts of Chemical Research·C David Sherrill
Nov 18, 2015·Journal of Chemical Theory and Computation·Ka Un LaoJohn M Herbert
Aug 15, 2013·The Journal of Physical Chemistry Letters·Ryan M RichardJohn M Herbert
Aug 9, 2013·The Journal of Physical Chemistry. B·Kay AnsorgBernd Engels
Sep 11, 2018·Journal of Chemical Theory and Computation·Ka Un Lao, John M Herbert
Dec 10, 2021·Journal of Chemical Theory and Computation·Francisco Ballesteros, Ka Un Lao

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