Potential energy functions for an intramolecular proton transfer reaction in the ground and excited state

We describe the development of empirical potential functions for the study of the excited state intramolecular proton transfer reaction in 1-(trifuloroacetylamino)naphtaquinone (TFNQ). The potential is a combination of the standard CHARMM27 force field for the backbone structure of TFNQ and an empirical valence bond formalism for the proton transfer reaction. The latter is parameterized to reproduce the potential energies both in the ground and the excited state, determined at the CASPT2 level of theory. Parameters describing intermolecular interactions are fitted to reproduce molecular dipole moments computed at the CASSCF level of theory and to reproduce ab initio hydrogen bonding energies and geometries for TFNQ-water bimolecular complexes. The utility of this potential energy function was examined by computing the potentials of mean force for the proton transfer reactions in the gas phase and in water, in both electronic states. The ground state PMF exhibits little solvent effects, whereas computed potential of mean force shows a solvent stabilization of 2.5 kcal mol−1 in the product state region, suggesting proton transfer is more pronounced in polar solvents, consistent with experimental findings. Electronic supplementary material The online version of this article (doi:10.1007/s00214-007-0272-z) contains supplementary material, which is available to authorized users. Contribution to the Fernando Bernardi Memorial Issue. A. Cembran · J. Gao (B) Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA e-mail: [email protected]