Effects of the second hydration shell on excited-state multiple proton transfer: dynamics simulations of 7-azaindole:(H2O)1–5 clusters in the gas phase

  • Nawee KungwanEmail author
  • Khanittha Kerdpol
  • Rathawat Daengngern
  • Supa Hannongbua
  • Mario BarbattiEmail author
Regular Article
Part of the following topical collections:
  1. Shavitt Memorial Festschrift Collection


Dynamics of the multiple excited-state proton transfer (ESPT) in clusters of 7-azaindole with up to five water molecules was investigated with quantum chemical methods. The ultrafast excited-state dynamics triggered by photoexcitation was simulated with the algebraic diagrammatic construction to the second-order scheme. Multiple ESPT through a hydrogen-bonded network is observed in the 100-fs scale. The probability of tautomerization is anti-correlated with the maximum free energy barrier in the excited state. An increasing number of water molecules tends to reduce the barrier by strengthening the hydrogen-bonded network. Barrierless reactions are found already for clusters with four waters. In structures presenting double hydrogen bond circuits, proton transfer happens mostly through the internal circuit by triple proton transfer. The overall role of the second hydration shell is of stabilizing the network, facilitating the proton transfer in the internal circuit. Proton transfers involving the second hydration shell were observed, but with small probability of occurrence. The proton-transfer processes tend to be synchronous, with two of them occurring within 10–15 fs apart.


On-the-fly dynamics simulation Excited-state proton transfer Excited-state tautomerization Water-assisted proton transfer Hydrogen bond rearrangement 7-Azaindole ADC(2) 



The authors wish to thank the Thailand Research Fund (MRG5480294 and TRG5680098) for financial support. K. Kerdpol and R. Daengngern thank the Science Achievement Scholarship of Thailand (SAST), Faculty of Science, Chiang Mai University, Chiang Mai, Thailand.

Supplementary material

214_2014_1480_MOESM1_ESM.pdf (2.6 mb)
Ground-state structures of the 7AI(H2O) n=1,1+1,2 complexes; snapshots of trajectories featuring HBR and tautomerization; time evolution of average potential energies and average bond lengths; average relative energies along the reaction pathways; relative energies of the three ground-state 7AI(H2O)3 isomers; Cartesian coordinates of all investigated complexes. (PDF 2693 kb)


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Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  1. 1.Department of Chemistry, Faculty of ScienceChiang Mai UniversityChiang MaiThailand
  2. 2.Department of Chemistry, Faculty of ScienceKasetsart UniversityBangkokThailand
  3. 3.Max-Planck-Institut für KohlenforschungMülheim an der RuhrGermany

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