Quantum mechanical valence study of a bond-breaking–bond-forming process in triatomic systems

The recently introduced set of the quadratic, two-electron covalent and ionic valence indices is used to investigate the bond-breaking–bond-forming (BB-BF ) process in an atom exchange reaction between H₂ and X (X = H, F—I) as well as in the O₂—H system. Valence changes accompanying selected charge reorganizations are examined within the three-orbital model and valence diagrams for symmetric transition states (TS s) are given. The UHF valence data for Li₂O and CO₂ and the H—H—X, O—O—H, and O—H—O (ABC) TS s (collinear and angular) are reported and compared to valence data in the separated fragments limits (SFL ), AB and BC. The overall valence, ν(ABC), and the total (ionic plus covalent) diatomic valences, ν_AB and ν_BC, are used as measures of the overall bond-order in a concerted BB–BF reaction, to test the postulate of the bond-energy–bond-order (BEBO ) model. In collinear TS s of H₂X, ν ? ?1, i.e., one bonding electron pari, is found to be roughly preserved, whereas in the angular H₂X and in collinear O—H—O TS s, the effect of increased valence at the saddle-point is observed, relative to that of diatomic fragments (reactiants or products). For the angular O—O—H TS , a similar increase in | ν (ABC)| relative to both O₂ and OH SFL s is detected; smaller changes relative to the O₂ data are found in the collinear TS . This observation is in agreement with earlier predictions from the intersecting-state model. The relative diatomic valences, ν/ν and ν/ν, are shown to conserve the overall relative bond multiplicity around 1 in both collinear and angular TS s of the H₂—X systems. © 1994 John Wiley & Sons, Inc.