Abstract
To accurately predict the free energy barrier for urea elimination in aqueous solution, we examined the reaction coordinates for the direct and water-assisted elimination pathways, and evaluated the corresponding free energy barriers by using the surface and volume polarization for electrostatics (SVPE) model-based first-principles electronic-structure calculations. Based on the computational results, the water-assisted elimination pathway is dominant for urea elimination in aqueous solution, and the corresponding free energy barrier is 25.3 kcal/mol. The free energy barrier of 25.3 kcal/mol predicted for the dominant reaction pathway of urea elimination in aqueous solution is in good agreement with available experimental kinetic data.
| Original language | English |
|---|---|
| Pages (from-to) | 143-146 |
| Number of pages | 4 |
| Journal | Chemical Physics Letters |
| Volume | 625 |
| DOIs | |
| State | Published - Apr 1 2015 |
Bibliographical note
Funding Information:This work was supported in part by the NSF (grant CHE-1111761 to Zhan), the NIH (grants R01 DA035552, R01 DA032910, R01 DA013930 and R01 DA025100 to Zhan), and the National Natural Science Foundation of China (grant No. 21273089 ). Yao worked in Zhan's laboratory for this project at the University of Kentucky as an exchange graduate student supported by the China Scholarship Council. The authors also acknowledge the Computer Center at the University of Kentucky for supercomputing time on a Dell X-series Cluster with 384 nodes or 4768 processors.
Publisher Copyright:
© 2015 Elsevier B.V. All rights reserved.
ASJC Scopus subject areas
- Physics and Astronomy (all)
- Physical and Theoretical Chemistry