title: Bond dissociation energies of C10 and C18 methyl esters from local multireference averaged-coupled pair functional theory.
abstract: We previously developed a fast, local, reduced scaling Cholesky-decomposed multireference averaged-coupled pair functional (CD-LMRACPF2) method, which takes advantage of the locality of dynamic correlation and numerical approximations such as Cholesky decomposition and integral screening. Motivated by the desire to study large biodiesel methyl ester molecules, here we validate CD-LMRACPF2 for the computation of bond dissociation energies (BDEs) in a suite of oxygenated molecules, and show that the low-cost method is very accurate compared to the conventional variant. We then demonstrate the power of CD-LMRACPF2 for fast and accurate computation of energies of molecules containing up to 13 second-row atoms within a polarized triple-ζ (cc-pVTZ) basis set. We use biodiesel methyl esters as a chemically interesting model system and furnish BDEs of C10 and C18 methyl esters, with the latter performed within a cc-pVDZ basis set. We describe trends in the BDEs and explain how structural (isomeric) differences affect BDEs, as well as discuss implications of BDE trends for biodiesel physical and chemical properties.
authors.affiliation: †Departments of Chemical and Biological Engineering, ‡Mechanical and Aerospace Engineering, §Chemistry, ∥Program in Applied and Computational Mathematics, and ⊥Andlinger Center for Energy and the Environment, Princeton University, Princeton, New Jersey, 08544, United States.
authors.forename: Victor B
authors.initials: VB
authors.lastname: Oyeyemi
authors.affiliation: †Departments of Chemical and Biological Engineering, ‡Mechanical and Aerospace Engineering, §Chemistry, ∥Program in Applied and Computational Mathematics, and ⊥Andlinger Center for Energy and the Environment, Princeton University, Princeton, New Jersey, 08544, United States.
authors.forename: Johannes M
authors.initials: JM
authors.lastname: Dieterich
authors.affiliation: †Departments of Chemical and Biological Engineering, ‡Mechanical and Aerospace Engineering, §Chemistry, ∥Program in Applied and Computational Mathematics, and ⊥Andlinger Center for Energy and the Environment, Princeton University, Princeton, New Jersey, 08544, United States.
authors.forename: David B
authors.initials: DB
authors.lastname: Krisiloff
authors.affiliation: †Departments of Chemical and Biological Engineering, ‡Mechanical and Aerospace Engineering, §Chemistry, ∥Program in Applied and Computational Mathematics, and ⊥Andlinger Center for Energy and the Environment, Princeton University, Princeton, New Jersey, 08544, United States.
authors.forename: Ting
authors.initials: T
authors.lastname: Tan
authors.affiliation: †Departments of Chemical and Biological Engineering, ‡Mechanical and Aerospace Engineering, §Chemistry, ∥Program in Applied and Computational Mathematics, and ⊥Andlinger Center for Energy and the Environment, Princeton University, Princeton, New Jersey, 08544, United States.
authors.forename: Emily A
authors.initials: EA
authors.lastname: Carter
mesh_terms: D004952:Esters / Q000737:chemistry*; D015394:Molecular Structure; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D004952:Esters