Thermochemistry of organic reactions in microporous oxides by atomistic simulations: benchmarking against periodic B3LYP.
The methylation of ethene by methyl chloride and methanol in the microporous materials SAPO-34 and SSZ-13 has been studied using different periodic atomistic modeling approaches based on density functional theory. The RPBE functional, which earlier has been used successfully in studies of surface reactions on metals, fails to yield a qualitatively correct description of the transition states under study. Employing B3LYP as functional gives results in line with experimental data: (1) Methanol is adsorbed more strongly than methyl chloride to the acid site. (2) The activation energies for the methylation of ethene are slightly lower for SSZ-13. Furthermore, the B3LYP activation energies are lower for methyl chloride than for methanol.
Bleken
Francesca
F
inGAP Center of Research Based Innovation, Department of Chemistry, University of Oslo, P. O. Box 1033 Blindern, N-0315 Oslo, Norway.
Svelle
Stian
S
Lillerud
Karl Petter
KP
Olsbye
Unni
U
Arstad
Bjørnar
B
Swang
Ole
O
D000327:Adsorption; D000432:Methanol / Q000737:chemistry*; D008737:Methyl Chloride / Q000737:chemistry*; D008745:Methylation; D008956:Models, Chemical; D056004:Molecular Dynamics Simulation; D010087:Oxides / Q000737:chemistry*; D016062:Porosity; D013499:Surface Properties; D013816:Thermodynamics
D010087:Oxides; D008737:Methyl Chloride; D000432:Methanol