USING ENERGY DERIVATIVES TO FIND STATIONARY POINTS OF POTENTIAL ENERGY SURFACES

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1986

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Ohio State University

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A simple method for using energy derivatives to find stationary points on molecular potential energy surfaces is described. It is based on a least aquares fit of the energy and energy derivative data to a polynomial expressed in a minimal subset of the cartesian coordinetes of the atoms. Stationary points of this polynomial surface are used to predict the position of stationary points of the molecular surface. These points are used for additional electronic energy calculations and the procedure is iterated to convergence. For calculating frequencies, the polynomial Hessian is transformed back to cartesian coordinates of the atoms for case of mass-weighting. This method was used to optimize the SCF geometry of $CH^{+}_{5}$ in $C_{*}$ symmetry. Significant relaxation of the $CH_{3}$ portion was observed, in comparison with previous calculations in which that portion was constrained to $C_{3v}$ geometry. The calculated frequencies are reported.

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Address: Department of Chemistry, The Ohio State University, Columbus OH 43210
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