Electrostatic catalysis molecular potentials

AMI AMBER A Program for Simulation of Biological and Organic Molecules CHARMM The Energy Function and Its Parameterization Combined Quantum Mechanics and Molecular Mechanics Approaches to Chemical and Biochemical Reactivity Density Functional Theory (DFT), Hartree-Fock (HF), and the Self-consistent Field Divide and Conquer for Semiempirical MO Methods Electrostatic Catalysis Force Fields A General Discussion Force Fields CFF GROMOS Force Field Hybrid Methods Hybrid Quantum Mechanical/Molecular Mechanical (QM/MM) Methods Mixed Quantum-Classical Methods MNDO MNDO/d Molecular Dynamics Techniques and Applications to Proteins OPLS Force Fields Parameterization of Semiempirical MO Methods PM3 Protein Force Fields Quantum Mechanical/Molecular Mechanical (QM/MM) Coupled Potentials Quantum Mecha-nics/Molecular Mechanics (QM/MM) SINDOI Parameterization and Application. 

One of the simplest examples of electrostatic catalysis is the acceleration of the 1,5-hydride shift in cyclopentadiene by the influence of Li" " cations. The reaction proceeds via an asymmetric transition state that is 34 kJ mol more stable than the symmetric ground state. It could be shown that this extra stabilization (catalytic rate acceleration) is completely due to the effect of the electrostatically bound cation. Difference in cation complexation energies could be adequately illustrated by molecular electrostatic potential (MEP) maps for the ground and transition states (see Electrostatic Potentials Chemical Applications). The maps are symmetric and asymmetric for the ground and transition states, respectively, and indicate larger cation attraction for the latter. 

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