Advanced Review Geometry optimization（高级评审几何优化）.pdf

Advanced Review Geometry optimization H. Bernhard Schlegel∗ Geometry optimization is an important part of most quantum chemical calcu- lations. This article surveys methods for optimizing equilibrium geometries, lo- cating transition structures, and following reaction paths. The emphasis is on optimizations using quasi-Newton methods that rely on energy gradients, and the discussion includes Hessian updating, line searches, trust radius, and rational function optimization techniques. Single-ended and double-ended methods are discussed for transition state searches. Single-ended techniques include quasi- Newton, reduced gradient following and eigenvector following methods. Double- ended methods include nudged elastic band, string, and growing string methods. The discussions conclude with methods for validating transition states and fol- lowing steepest descent reaction paths. C 2011 John Wiley Sons, Ltd. WIREs Comput Mol Sci 2011 1 790–809 DOI: 10.1002/wcms.34 INTRODUCTION be reviewed elsewhere in this series. Global mapping eometry optimization is a key component of of reaction networks21 ,22 is outside the scope of this Gmost computational chemistry studies that are chapter. Transition path sampling and reaction paths concerned with the structure and/or reactivity of on free energy surfaces are also not covered.23 Dis- molecules. This chapter describes some of the meth- cussions of optimization methods to find conical in- ods that are used to optimize equilibrium geometries, tersections and minimum energy seam crossings can locate transition str