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Chirality recognition in concerted proton transfer process for prismatic water clusters

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Abstract

Proton transfer and chiral conversion via hydrogen bonds (HBs) are important processes in applications such as chiral recognition, enzymatic catalysis, and drug preparation. Herein, we investigate the chiral conversion and interlayer recognition, via concerted intralayer proton transfer (CIPT) processes, of small prismatic water clusters, in the form of bilayer n−membered water rings (BnWRs, n = 4, 5, 6). Density functional theory (DFT) calculations show that despite the small energy variations between the initial and final states of the clusters of less than 0.3 kcal·mol−1, the vibrational circular dichroism (VCD) spectrum provides clear chiral recognition peaks in the range of 3,000 to 3,500 cm−1. The vibrational modes in this region correspond to stretching of intralayer HBs, which produces strong signals in the infrared (IR) and Raman spectra. The electronic circular dichroism (ECD) spectrum also reveals obvious chiroptical characteristics. The molecular orbitals involved in the interlayer interaction are dominated by O 2p atomic orbitals; the energy of these orbitals increased by up to 0.1 eV as a result of the CIPT processes, indicating corresponding recognition between monolayer water clusters. In addition, isotopic substitution by deuterium in the BnWRs results in characteristic peaks in the VCD spectra that can be used as fingerprints in the identification of the chiral structures. Our findings provide new insights into the mechanism of chiral recognition in small prismatic water clusters at the atomic level as well as incentives for future experimental studies.

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Authors and Affiliations

  1. Institute of Atomic and Molecular Physics, Jilin University, Changchun, 130012, China

    Bo Wang, Wanrun Jiang, Yang Gao & Zhigang Wang

  2. Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun, 130012, China

    Bo Wang, Wanrun Jiang, Yang Gao & Zhigang Wang

  3. College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China

    Boon K. Teo

  4. College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

    Boon K. Teo

  5. Beijing Computational Science Research Center, Beijing, 100084, China

    Zhigang Wang

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Wang, B., Jiang, W., Gao, Y. et al. Chirality recognition in concerted proton transfer process for prismatic water clusters. Nano Res. 9, 2782–2795 (2016). https://doi.org/10.1007/s12274-016-1167-x

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