Predissociation Measurements of Bond Dissociation Energies

A fundamental need in chemistry is understanding the chemical bond, for which the most quantitative measure is the bond dissociation energy (BDE). While BDEs of chemical bonds formed from the lighter main group elements are generally well-known and readily calculated by modern computational chemistry, chemical bonds involving the transition metals, lanthanides, and actinides remain computationally extremely challenging. This is due to the simultaneous importance of electron correlation, spin-orbit interaction, and other relativistic effects, coupled with the large numbers of low-lying states that are accessible in systems with open d or f subshells. The development of efficient and accurate computational methods for these species is currently a major focus of the field. An obstacle to this effort has been the scarcity of highly precise benchmarks for the BDEs of M-X bonds. For most of the transition metal, lanthanide, or actinide systems, tabulated BDEs of M-X bonds have been determined by Knudsen effusion mass spectrometric measurements of high-temperature equilibria. The measured ion signals are converted to pressures and activities of the species involved in the equilibrium, and the equilibrium constants are then analyzed using a van't Hoff plot or the third-law method to extract the reaction enthalpy, which is extrapolated to 0 K to obtain the BDE. This procedure introduces errors at every step and ultimately leads to BDEs that are typically uncertain by 2-20 kcal mol^-1 (0.1-1 eV). A second method in common use employs a thermochemical cycle in which the ionization energies of the MX molecule and M atom are combined with the BDE of the M⁺-X bond, obtained via guided ion beam mass spectrometry, to yield the BDE of the neutral, M-X. When accurate values of all three components of the cycle are available, this method yields good results-but only rarely are all three values available. We have recently implemented a new method for the precise measurement of BDEs in molecules with large densities of electronic states that is based on the rapid predissociation of these species as soon as the ground separated atom limit is exceeded. When a sharp predissociation threshold is observed, its value directly provides the BDE of the system. With this method, we are able in favorable cases to determine M-X BDEs to an accuracy of ∼0.1 kcal mol^-1 (0.004 eV). The method is generally applicable to species that have a high density of states at the ground separated atom limit and has been used to measure the BDEs of more than 50 transition metal-main group MX molecules thus far. In addition, a number of metal-metal BDEs have also been measured with this method. There are good prospects for the extension of the method to polyatomic systems and to lanthanide and actinide-containing molecules. These precise BDE measurements provide chemical trends for the BDEs across the transition metal series, as well as crucial benchmarks for the development of efficient and accurate computational methods for the d- and f-block elements.