Correlation between electron delocalization and structural planarization in small water rings |
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| Authors: | Bo Wang Li Wang Xing Dai Yang Gao Wanrun Jiang Jie Han Zhigang Wang Rui‐Qin Zhang |
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| Institution: | 1. Institute of Atomic and Molecular Physics, Jilin University, Changchun, China;2. Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun, China;3. Beijing Computational Science Research Center, Beijing, China;4. Department of Physics and Materials Science and Centre for Functional Photonics (CFP), City University of Hong Kong, Hong Kong SAR, China |
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| Abstract: | The discovery of the covalent‐like character of the hydrogen bonding (H‐bonding) system Science 342 , 611(2013)] has promoted a renewal of our understanding of the electronic and geometric structures of water clusters. In this work, based on density functional theory calculations, we show that the preferential formation of a stable quasiplanar structure of (H2O)n(n = 3–6) is closely related to three kinds of delocalized molecular orbitals (MOs; denoted as MO‐I, II, and III) of water rings. These originate from the 2p lone pair electrons of oxygen (O), the 2p bond electrons of O and the 1s electrons of H and the 2s electrons of O and 1s electrons of H, respectively. To maximize the orbital overlaps of the three MOs, geometric planarization is needed. The contribution of the orbital interaction is more than 30% in all the water rings according to our energy decomposition analysis, highlighting the considerable covalent‐like characters of H‐bonds. © 2015 Wiley Periodicals, Inc. |
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| Keywords: | hydrogen bonding electronic structure density functional theory quasiplanar structure molecular orbital |
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