Theoretical determination of molecular structure and conformation. 17. On the existence of FH/sub 2//sup -/, OH/sub 3//sup -/, NH/sub 4//sup -/, and CH/sub 5//sup -/ in the gas phase
Ab initio calculations (HF/6-31G* and MP2/6-31++G**) carried out for FH/sub 2//sup -/, OH/sub 3//sup -/, NH/sub 4//sup -/, and CH/sub 5//sup -/ indicate that these ions are most stable in the form of AH/sub n/-solvated H/sup -/ ions. Theoretical binding energies (42, 26, 15, and 6 kcal/mol) decrease with decreasing polarity of the AH bond. Apart from CH/sub 5//sup -/, all H/sup -/ x AH/sub n/ complexes can rearrange via internal proton transfer to AH/sub n-1//sup -/ x H/sub 2/ complexes which are 2-15 kcal/mol less stable than the former. Investigation of the various dissociation channels of AH/sub n+1//sup -/ ions reveals that NH/sub 4//sup -/, OH/sub 3//sup -/, and FH/sub 2//sup -/ are sufficiently stable in the gas phase to be detected by mass spectrometry. 36 references, 5 figures, 7 tables.
- Research Organization:
- Universitaet Koeln, West Germany
- OSTI ID:
- 5827947
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 90:1
- Country of Publication:
- United States
- Language:
- English
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ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMMONIUM COMPOUNDS
MOLECULAR STRUCTURE
ANIONS
CARBON COMPOUNDS
FLUORINE COMPOUNDS
HYDROGEN COMPOUNDS
BINDING ENERGY
CHEMICAL REACTION KINETICS
GASES
HARTREE-FOCK METHOD
HYDROGEN TRANSFER
THEORETICAL DATA
CHARGED PARTICLES
DATA
ENERGY
FLUIDS
HALOGEN COMPOUNDS
INFORMATION
IONS
KINETICS
NUMERICAL DATA
REACTION KINETICS
400201* - Chemical & Physicochemical Properties