Partition-DFT on the water dimer

As is well known, the ground-state symmetry group of the water dimer switches from its equilibrium C s -character to C 2h -character as the distance between the two oxygen atoms of the dimer decreases below R O–O ∼ 2.5 Å. For a range of R O–O between 1 and 5 Å, and for both symmetries, we apply Part...

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Bibliographic Details
Published in:The Journal of chemical physics 2017-02, Vol.146 (7), p.074106-074106
Main Authors: Gómez, Sara, Nafziger, Jonathan, Restrepo, Albeiro, Wasserman, Adam
Format: Article
Language:English
Subjects:
Chemistry
Deformation
Density functional theory
Dimers
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Monomers
Oxygen atoms
Partitions
Physics
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Summary:As is well known, the ground-state symmetry group of the water dimer switches from its equilibrium C s -character to C 2h -character as the distance between the two oxygen atoms of the dimer decreases below R O–O ∼ 2.5 Å. For a range of R O–O between 1 and 5 Å, and for both symmetries, we apply Partition Density Functional Theory (PDFT) to find the unique monomer densities that sum to the correct dimer densities while minimizing the sum of the monomer energies. We calculate the work involved in deforming the isolated monomer densities and find that it is slightly larger for the C s geometry for all R O–O. We discuss how the PDFT densities and the corresponding partition potentials support the orbital-interaction picture of hydrogen-bond formation.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4976306