Fixed-node diffusion Monte Carlo shows promise for modeling reaction thermochemistry of hydrocarbon-based radicals

Reliable thermodynamic and kinetic properties of free radical polymerization reactions are essential for synthesizing both primary polymeric materials and specialty polymers. The computational generation of these data from quantum chemistry requires a time-efficient method capable of capturing the e...

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Bibliographic Details
Published in:The Journal of chemical physics 2024-07, Vol.161 (3)
Main Authors: Huber, Timothy B., Wheeler, Ralph A.
Format: Article
Language:English
Subjects:
Chemical reactions
Chemical synthesis
Enthalpy
Ethylene
Free radical polymerization
Free radicals
Hydrogen
Methyl radicals
Polymerization
Quantum chemistry
Thermochemistry
Wave functions
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Summary:Reliable thermodynamic and kinetic properties of free radical polymerization reactions are essential for synthesizing both primary polymeric materials and specialty polymers. The computational generation of these data from quantum chemistry requires a time-efficient method capable of capturing the essential physics. One such method, fixed-node diffusion Monte Carlo (FN-DMC) (using single Slater–Jastrow trial wavefunctions), has demonstrated the capability to recover 90%–95% of missing dynamic correlation energy for typical systems. In this study, methyl radical addition to ethylene serves as a simple model to test FN-DMC’s ability to calculate enthalpies of reaction and activation energies with different time steps, antisymmetric trial wavefunctions, basis set sizes, and effective core potentials. The FN-DMC computational protocol thus defined for methyl radical addition to ethylene is subsequently benchmarked against Weizmann-1 and experimental reaction enthalpies from Lin et al.’s test set of 21 radical addition and 28 hydrogen abstraction enthalpies. Our findings reveal that FN-DMC consistently generates reaction enthalpies with chemical accuracy, exhibiting mean absolute deviation of 3.5(7) and 1.4(8) kJ/mol from the Weizmann-1 reference for radical addition and hydrogen abstraction reactions, respectively. Given its favorable computational scaling and high degree of parallelizability, we, therefore, recommend more comprehensive testing of FN-DMC with effective core potentials to address more extensive and intricate polymerization reactions and reactions with other radicals.
ISSN:0021-9606
1089-7690
1089-7690
DOI:10.1063/5.0211903