Efficient determination and characterization of transition states using ab-initio methods

Abstract The gradient of the potential energy with respect to nuclear coordinates has been calculated using ab-initio single determinant molecular orbital methods. The calculated gradient is used together with very efficient minimization methods to locate and characterize transition states on many-dimensional potential energy surfaces. Previously such methods have only been applied to semi-empirical potential functions. Although the calculation of the gradient in addition to the energy increases the computational time by about a factor of four, we have demonstrated the feasibility of these calculations by locating the transition state for the model rearrangement of HNC to HCN using both minimal (STO-3G) and split valence shell (4-31G) basis sets. Further use of such methods in the direct application of ab-initio wavefunctions to dynamical investigations is discussed.

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