1999/07/01 by Igor S. Ignatyev, Henry F. Schaefer · 1 citation
Chemistry · Physics and Astronomy · Chemical Engineering · #Inorganic Fluorides and Related Compounds #Advanced Chemical Physics Studies #Ammonia Synthesis and Nitrogen Reduction #Chemistry #Molecule #Dissociation (chemistry) #Bromine #Affinities #Electron affinity (data page) #Density functional theory #Halogen #Computational chemistry #Bond-dissociation energy #Ion #Crystallography #Atomic physics #Stereochemistry #Physical chemistry
paper · doi:10.1021/ja990144h
openalex publication_date 1999/07/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/06/26
Density functional methods were used for predictions of the structures and energetics of molecules and anions in the series BrClF n ( n = 1−5). Very little is known from experiment about these potentially important interhalogen molecules. Energy minima were found for all neutral molecules with the exception of BrClF 5 . However, the dissociation limits for ClF elimination from the BrClF 3 (BHLYP and B3LYP only) and BrClF 4 (all methods) molecules lie below the energy of the respective ground states. All the BrClF n anions are bound with respect to the corresponding neutrals; energy minima were found for anions up to BrClF 5 - . Structures of isomers with the chlorine atom in the central position were also optimized. However, these local minima lie substantially above the bromine-centered structures, and the energy gap between isomers grows with n . For the neutral molecules two paths of dissociation were found to possess the lowest energies, i.e., chlorine atom and ClF elimination. The latter channel becomes predominant at n > 1. For the anions the lowest energy dissociation pathways are Cl - or Cl elimination, but for n = 3, 5, ClF elimination becomes predominant. The adiabatic electron affinities, the vertical electron affinities of the BrClF n molecules, and the vertical detachment energies of the BrClF n - anions were predicted in this work. The adiabatic electron affinities of the closed-shell BrClF n molecules significantly exceed those of the corresponding BrF n species, while for molecules with an odd number of electrons they are similar or slightly lower than electron affinities in the BrF n series. Many new experiments are suggested by this researcher, in light of the large predicted electron affinities and the fact that none of these has been measured in the laboratory.