TY - JOUR
T1 - Correlation between electron delocalization and structural planarization in small water rings
AU - Wang, Bo
AU - Wang, Li
AU - Dai, Xing
AU - Gao, Yang
AU - Jiang, Wanrun
AU - Han, Jie
AU - Wang, Zhigang
AU - Zhang, Rui-Qin
PY - 2015/7/1
Y1 - 2015/7/1
N2 - 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.
AB - 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.
KW - density functional theory
KW - electronic structure
KW - hydrogen bonding
KW - molecular orbital
KW - quasiplanar structure
UR - http://www.scopus.com/inward/record.url?scp=84929655215&partnerID=8YFLogxK
UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-84929655215&origin=recordpage
U2 - 10.1002/qua.24897
DO - 10.1002/qua.24897
M3 - RGC 21 - Publication in refereed journal
VL - 115
SP - 817
EP - 819
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
SN - 0020-7608
IS - 13
ER -