Role of aromatic structure in pathways of hydrogen transfer and bond cleavage in coal liquefaction: Theoretical studies
- Pacific Northwest Lab., Richland, WA (United States)
- Univ. of Florida, Gainesville, FL (United States). Quantum Theory Project
The mechanisms by which strong carbon-carbon bonds between aromatic rings and side chains are cleaved under hydropyrolysis conditions remain a subject of wide interest to fuel science. Recently, the authors have studied in detail an alternate pathway for hydrogen atom transfer to {pi}-systems, radical hydrogen transfer (RHT). RHT is the direct, bimolecular transfer of hydrogen from the {beta}-position of an organic radical to the target {pi}-system. In the initial theoretical study, they examined the reaction ethyl radical + ethylene = ethylene + ethyl at the spin-projected UMP2/6-31G** level of theory. Recently, they have used a calibrated ROHF-MNDO-PM3 method to predict thermoneutral RHT barriers for hydrogen transfer between hydroaryl radicals and the corresponding arene. Because of the inherent limitations of semiempirical methods such as ROHF-MNDO-PM3, they have extended the initial work with the ethyl + ethylene study to examine this reaction at the ROHF-MBPT[2]-6-31G** and ROHF-CCSD[T]-6-31G** levels of ab initio theory. The primary objective was to determine how intrinsic RHT barriers change with conjugative stabilization of the radicals. The spin-restricted ROHF approach has been applied to study several RHT reactions, and they present completed ROHF results for the ethyl + ethylene system and preliminary results for the methallyl + butadiene system. The methallyl + butadiene system serves as a model for highly stabilized hydroaryl radicals: the methallyl radical exhibits a C-H bond strength of 46.5 kcal/mol compared to 9-hydroanthracenyl, 43.1 kcal/mol.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- AC06-76RL01830
- OSTI ID:
- 161454
- Report Number(s):
- PNL-SA-26307; CONF-950963-4; ON: DE96002481; TRN: AHC29601%%9
- Resource Relation:
- Conference: 8. international conference on coal science, Oviedo (Spain), 10-15 Sep 1995; Other Information: PBD: Sep 1995
- Country of Publication:
- United States
- Language:
- English
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