Degenerate intermolecular and intramolecular proton-transfer reactions: electronic structure of the transition states.
Density functional theory (DFT) calculations are performed on a series of double and single proton-transfer reactions to study the variation in polarizations in complexes during the dynamics of proton transfer from one isoenergetic, hydrogen-bonded ground-state structure to the other. The isotropic average polarizability (alpha(av)) shows an interesting single-humped profile with a maxima coinciding with the transition state of the reaction. Similar profiles are also computed at Nd:YaG frequencies. The origin of the maximal polarizability at the transition state is traced to maximal charge separation and large D (donor)-A (acceptor) distances. Maximal polarizability for the transition state suggests an interesting, novel, and less memory extensive computational tool to locate the transition state for hydrogen-transfer reactions in hydrogen-bonded complexes.
Mandal
Tarun K
TK
Pati
Swapan K
SK
Datta
Ayan
A
D015057:1-Naphthylamine / Q000031:analogs & derivatives / Q000737:chemistry; D019342:Acetic Acid / Q000737:chemistry; D019281:Dimerization; D004583:Electrons; D005561:Formates / Q000737:chemistry; D006860:Hydrogen Bonding; D008958:Models, Molecular; D008968:Molecular Conformation; D011522:Protons; D011789:Quantum Theory; D014269:Trifluoroacetic Acid / Q000737:chemistry
D005561:Formates; D011522:Protons; C030544:formic acid; C418992:1,8-bis(dimethylamino)naphthalene; D015057:1-Naphthylamine; D014269:Trifluoroacetic Acid; D019342:Acetic Acid