The vibrational motions of a molecule in its equilibrium or during a chemical reaction provide
a wealth of information about its structure, stability, and reactivity. This information is hidden …

Computational approaches to understanding chemical reaction mechanisms generally
begin by establishing the relative energies of the starting materials, transition state, and …

The unified reaction valley approach (URVA) used for a detailed mechanistic analysis of
chemical reactions is improved in three different ways:(i) Direction and curvature of path are …

The bond energy (BE) of a polyatomic molecule cannot be measured and, therefore,
determination of BEs can only be done within a model using a set of assumptions. The bond …

We discuss the physical criteria that have been proposed as a measure of the strength of a
chemical bond. Critical examination of the strengths and weaknesses of the various …

Conspectus Mode specificity is defined by the differences in reactivity due to excitations in
various reactant modes, while bond selectivity refers to selective bond breaking in a …

Ab initio calculations give, with an accuracy depending on the sophistication of the method,
a bond length as an equilibrium value, r e. The experimental bond lengths are always …

One of the major goals of chemistry is to control chemical reactions with the purpose of
generating new compounds with useful properties. Control of a chemical reaction implies a …

Molecular vibrations drive chemical reactions. Because reaction requires a rearrangement
of nuclear positions as old bonds break and new ones form, a few molecules that have …

It has been long established that the transition state for an activated reaction controls the
overall reactivity, serving as the bottleneck for reaction flux. However, the role of the …