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. 2016 Feb 24:6:22099.
doi: 10.1038/srep22099.

Molecular orbital analysis of the hydrogen bonded water dimer

Bo Wang  1   2 , Wanrun Jiang  1   2 , Xin Dai  1   2 , Yang Gao  1   2 , Zhigang Wang  1   2   3 , Rui-Qin Zhang  4
Affiliations

Molecular orbital analysis of the hydrogen bonded water dimer

Bo Wang et al. Sci Rep. .

Erratum in

Abstract

As an essential interaction in nature, hydrogen bonding plays a crucial role in many material formations and biological processes, requiring deeper understanding. Here, using density functional theory and post-Hartree-Fock methods, we reveal two hydrogen bonding molecular orbitals crossing the hydrogen-bond's O and H atoms in the water dimer. Energy decomposition analysis also shows a non-negligible contribution of the induction term. Our finding sheds light on the essential understanding of hydrogen bonding in ice, liquid water, functional materials and biological systems.

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Figures

Figure 1
Figure 1. The equilibrium structure of (H2O)2.
Figure 2
Figure 2. The orbital interaction diagram of (H2O)2.
Orbital energy levels are represented as solid bars. The bars on the left and right sides correspond to the FOs of the two water monomers; the bars in the middle correspond to the complex orbitals of (H2O)2. The topmost solid black bars denote the highest occupied MOs (HOMOs). Blue solid bars denote two H-bonding MOs between the two water monomers, HOMO-2 and HOMO-4. Two corresponding bars are linked by short red dotted lines in the center of which the component percentage values (%) are given for those with the composition of a FO in a complex orbital larger than 0.5%.
Figure 3
Figure 3
The component percentages of fragment orbitals in the two crossing complex MOs(HOMO-2 (a) and HOMO-4 (b)), respectively. The Mos of (H2O)2 are obtained at different levels ofbasis sets through single point calculations at aug-cc-pVXZ (X = D, T, Q, 5 and 6) levels of theory. The symbol C, D and A represent the complex, donor and acceptor waters, respectively. The “homo” denotes the HOMO of water monomer.
Figure 4
Figure 4. Energy and percentage values of (H2O)2 at different O…H distances (DO…H).
(a) Interaction, electrostatic, exchange, induction, and dispersion energies of (H2O)2 at different O…H distances (DO…H). (b) The percentage values represent contribution to the total attractive interactions. The black dotted lines represent the equilibrium O…H distance of (H2O)2.
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References

    1. Cobar E. A., Horn P. R., Bergman R. G. & Head-Gordon M. Examination of the hydrogen-bonding networks in small water clusters (n = 2–5, 13, 17) using absolutely localized molecular orbital energy decomposition analysis. Phys. Chem. Chem. Phys. 14, 15328–15339 (2012). - PubMed
    1. Meng X. et al. Direct visualization of concerted proton tunnelling in a water nanocluster. Nat. Phys. 11, 235–239 (2015).
    1. Drechsel-Grau C. & Marx D. Tunnelling in chiral water clusters: Protons in concert. Nat.Phys. 11, 216–218 (2015).
    1. Warshel A. et al. Electrostatic basis for enzyme catalysis. Chem. Rev. 106, 3210–3235 (2006). - PubMed
    1. Gerlt J. A., Kreevoy M. M., Cleland W. W. & Frey P. A. Understanding enzymic catalysis: the importance of short, strong hydrogen bonds. Chem. Biol. 4, 259–267 (1997). - PubMed

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