A Variational Approach to London Dispersion Interactions without Density Distortion

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

We introduce a class of variational wave functions that captures the long-range interaction between neutral systems (atoms and molecules) without changing the diagonal of the density matrix of each monomer. The corresponding energy optimization yields explicit expressions for the dispersion coefficients in terms of the ground-state pair densities of the isolated systems, providing a clean theoretical framework to build new approximations in several contexts. As the individual monomer densities are kept fixed, we can also unambiguously assess the effect of the density distortion on London dispersion interactions; for example, we obtain virtually exact dispersion coefficients between two hydrogen atoms up to C 10 and relative errors below 0.2% in other simple cases.

Original languageEnglish
Pages (from-to)1537-1541
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume10
Issue number7
DOIs
Publication statusPublished - 4 Apr 2019

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Monomers
Atoms
monomers
interactions
Wave functions
Ground state
Hydrogen
coefficients
hydrogen atoms
Molecules
wave functions
optimization
ground state
approximation
atoms
molecules
energy

Cite this

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title = "A Variational Approach to London Dispersion Interactions without Density Distortion",
abstract = "We introduce a class of variational wave functions that captures the long-range interaction between neutral systems (atoms and molecules) without changing the diagonal of the density matrix of each monomer. The corresponding energy optimization yields explicit expressions for the dispersion coefficients in terms of the ground-state pair densities of the isolated systems, providing a clean theoretical framework to build new approximations in several contexts. As the individual monomer densities are kept fixed, we can also unambiguously assess the effect of the density distortion on London dispersion interactions; for example, we obtain virtually exact dispersion coefficients between two hydrogen atoms up to C 10 and relative errors below 0.2{\%} in other simple cases.",
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A Variational Approach to London Dispersion Interactions without Density Distortion. / Kooi, Derk P.; Gori-Giorgi, Paola.

In: Journal of Physical Chemistry Letters, Vol. 10, No. 7, 04.04.2019, p. 1537-1541.

Research output: Contribution to JournalArticleAcademicpeer-review

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AB - We introduce a class of variational wave functions that captures the long-range interaction between neutral systems (atoms and molecules) without changing the diagonal of the density matrix of each monomer. The corresponding energy optimization yields explicit expressions for the dispersion coefficients in terms of the ground-state pair densities of the isolated systems, providing a clean theoretical framework to build new approximations in several contexts. As the individual monomer densities are kept fixed, we can also unambiguously assess the effect of the density distortion on London dispersion interactions; for example, we obtain virtually exact dispersion coefficients between two hydrogen atoms up to C 10 and relative errors below 0.2% in other simple cases.

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