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Chin. Phys. B, 2017, Vol. 26(10): 103401    DOI: 10.1088/1674-1056/26/10/103401

Combined multi-level quantum mechanics theories and molecular mechanics study of water-induced transition state of OH-+CO2 reaction in aqueous solution

Chen Li(李琛), Meixing Niu(牛美兴), Peng Liu(刘鹏), Yongfang Li(李永方), Dunyou Wang(王敦友)
College of Physics and Electronics, Shandong Normal University, Ji'nan 250014, China

The presence of a solvent interacting with a system brings about qualitative changes from the corresponding gas-phase reactions. A solvent can not only change the energetics along the reaction pathway, but also radically alter the reaction mechanism. Here, we investigated the water-induced transition state of the OH-+CO2→HCO3- reaction using a multi-level quantum mechanics and molecular mechanics method with an explicit water model. The solvent energy contribution along the reaction pathway has a maximum value which induces the highest energy point on the potential of mean force. The charge transfer from OH- to CO2 results in the breaking of the OH- solvation shell and the forming of the CO2 solvation shell. The loss of hydrogen bonds in the OH- solvation shell without being compensated by the formation of hydrogen bonds in the CO2 solvation shell induces the transition state in the aqueous solution. The calculated free energy reaction barrier at the CCSD(T)/MM level of theory, 11.8 kcal/mol, agrees very well with the experimental value, 12.1 kcal/mol.

Keywords:  transition state      reaction pathway      free energy barrier      solvent effect  
Received:  22 May 2017      Revised:  06 July 2017      Accepted manuscript online: 
PACS:  34.20.-b (Interatomic and intermolecular potentials and forces, potential energy surfaces for collisions)  
  34.20.Cf (Interatomic potentials and forces)  
  34.20.Gj (Intermolecular and atom-molecule potentials and forces)  
  34.50.Lf (Chemical reactions)  

Project supported by the National Natural Science Foundation of China (Grant No. 11374194) and Taishan Scholarship Fund from Shandong Province, China.

Corresponding Authors:  Dunyou Wang     E-mail:

Cite this article: 

Chen Li(李琛), Meixing Niu(牛美兴), Peng Liu(刘鹏), Yongfang Li(李永方), Dunyou Wang(王敦友) Combined multi-level quantum mechanics theories and molecular mechanics study of water-induced transition state of OH-+CO2 reaction in aqueous solution 2017 Chin. Phys. B 26 103401

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