Deprotonation of solvated formic acid: Car-Parrinello and metadynamics simulations.
The deprotonation of solvated formic acid was investigated theoretically with ab initio simulations. With the Car-Parrinello method, deprotonation and reprotonation by means of a proton wire were observed. The microscopics of these reactions were analyzed, and reveal the key role played by nearby water molecules in catalyzing the reactions. A constrained molecular dynamics calculation was carried out to estimate the dissociation free energy. Deprotonation of formic acid was further investigated with the recently developed metadynamics method using the formic acid oxygen coordination numbers as the collective variables. The determined free-energy landscape gives barriers similar to that obtained with the constrained free-energy calculation.
Center for High Performance Simulations (CHiPS) and Department of Physics, North Carolina State University, Raleigh, North Carolina 27695, USA.
Jung-Goo
JG
Lee
Eliana
E
Asciutto
Volodymyr
V
Babin
Celeste
C
Sagui
Thomas
T
Darden
Christopher
C
Roland
D019295:Computational Biology; D003198:Computer Simulation; D005561:Formates / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry; D011522:Protons; D012997:Solvents / Q000737:chemistry*; D013816:Thermodynamics; D013997:Time Factors
D005561:Formates; D011522:Protons; D012997:Solvents; C030544:formic acid; D006859:Hydrogen; D010100:Oxygen