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Hydrogen Bond Cooperativity and the Three‐Dimensional Structures of Water Nonamers and Decamers
Author(s) -
Pérez Cristóbal,
Zaleski Daniel P.,
Seifert Nathan A.,
Temelso Berhane,
Shields George C.,
Kisiel Zbigniew,
Pate Brooks H.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201407447
Subject(s) - cooperativity , hydrogen bond , chemistry , cluster (spacecraft) , molecule , crystallography , hydrogen , water cluster , binding energy , bond length , low barrier hydrogen bond , chemical physics , computational chemistry , atomic physics , crystal structure , physics , organic chemistry , biochemistry , computer science , programming language
Broadband rotational spectroscopy of water clusters produced in a pulsed molecular jet expansion has been used to determine the oxygen atom geometry in three isomers of the nonamer and two isomers of the decamer. The isomers for each cluster size have the same nominal geometry but differ in the arrangement of their hydrogen bond networks. The nearest neighbor OO distances show a characteristic pattern for each hydrogen bond network isomer that is caused by three‐body effects that produce cooperative hydrogen bonding. The observed structures are the lowest energy cluster geometries identified by quantum chemistry and the experimental and theoretical OO distances are in good agreement. The cooperativity effects revealed by the hydrogen bond OO distance variations are shown to be consistent with a simple model for hydrogen bonding in water that takes into account the cooperative and anticooperative bonding effects of nearby water molecules.