Diabatic ordering of vibrational normal modes in reaction valley studies

Abstract

Diabatic ordering of the normal model of a reaction complex along the reaction path has several advantages with regard to adiabatic ordering. The method is based on rotations of the vibrational normal modes at one point, s, of the reaction path to maximize overlap with the vibrational modes at a neighboring point. Global rotations precede the rotations of degenerate modes so that changes in the direction of the reaction path and changes in the force constant matrix, which represent the two major effects for changes in mode ordering, can be separated. Overlap criteria identify resolved and unresolved avoided crossings of normal modes of the same symmetry. Diabatic mode ordering (DMO) can be used to resolve the latter by reducing the step size, thus guaranteeing correct ordering of normal modes in dependence of s. DMO is generally applicable to properties of the reaction complex that depend on s such as normal mode frequencies, orbital energies, the energy of excited states, etc. Additional applications are possible using a generalized reaction path vector, which may describe the change in atom masses, geometrical parameters, and/or the force constant matrix. In this way, the vibrational spectra of isotopomers can be investigated or the vibrational frequencies of different molecules correlated. © 1997 John Wiley & Sons, Inc. J Comput Chem 18: 1282–1294, 1997