Thermochemical properties of exo-tricyclo[5.2.1.0(2,6)]decane (JP-10 jet fuel) and derived tricyclodecyl radicals.
exo-Tricyclo[5.2.1.0(2,6)]decane (TCD) or exo-tetrahydrodicyclopentadiene is the principal component of the high-energy density hydrocarbon fuel commonly identified as JP-10. Thermodynamic parameters for the parent TCD molecule and of all the tricyclodecyl radicals corresponding to the loss of hydrogen atoms from different carbons sites (TCD-Ri with i indicating the given carbon center) are determined using several density functional theory and G3MP2B3 and CBS-QB3 higher level composite computational chemistry methods. Five isodesmic work reactions, three involving bridged hydrocarbon reference molecules with similar ring strains, are employed to produce a cancelation of systematic calculation errors in evaluation of standard, gas-phase formation enthalpies at 298 K. Delta(f)H degrees (298) for TCD is found to be -19.5 +/- 1.3 kcal mol(-1), which is several kcal mol(-1) lower than the commonly used values. C(i)-H bond energies for corresponding TCD carbon sites are evaluated as follows: TCD-R1, 107.2; TCD-R2, 100.1; TCD-R3, 98.0; TCD-R4, 98.5; TCD-R9, 98.7; TCD-R10, 104.1 kcal mol(-1). Results from use of five different DFT methods are in very good agreement with composite level values for all work reactions used for the radicals. The exo and endo isomers of TCD are both determined to have chair and boat conformers.
Hudzik
Jason M
JM
Chemistry, Chemical Engineering and Environmental Science, New Jersey Institute of Technology, Newark, New Jersey 07102, USA.
Asatryan
Rubik
R
Bozzelli
Joseph W
JW
D005609:Free Radicals / Q000737:chemistry; D006575:Heterocyclic Compounds, 3-Ring / Q000737:chemistry*; D007189:Indans / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D013816:Thermodynamics
D005609:Free Radicals; D006575:Heterocyclic Compounds, 3-Ring; D007189:Indans; C038457:octahydro-exo-4,7-methano-1H-indene