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Joel Leitão Nascimento1, Maiara Oliveira Passos1, Tiago Vinicius Alves1

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This study calculates thermal rate constants for methyl pentanoate reactions using advanced computational methods. Truncating conformational data significantly impacts accuracy, leading to potential errors up to 75%.

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Area of Science:

  • Chemical Kinetics
  • Computational Chemistry

Background:

  • Hydrogen abstraction reactions are crucial in chemical processes.
  • Accurate calculation of thermal rate constants is essential for understanding reaction dynamics.

Purpose of the Study:

  • To calculate thermal rate constants for the hydrogen abstraction reaction of methyl pentanoate.
  • To investigate the impact of conformational analysis on theoretical rate constant calculations.

Main Methods:

  • Utilized multistructural canonical variational theory with small-curvature tunneling (MS-CVT/SCT).
  • Employed a combined systematic and stochastic search algorithm for conformational analysis.
  • Performed high-level electronic structure calculations (MPWB1K/6-31+G(d,p)).

Main Results:

  • Identified 244 unique geometries for methyl pentanoate and associated transition states.
  • Demonstrated that rotation around the ester's -OCH3 group yields unstable structures with minimal contribution to partition functions.
  • Quantified that truncating multistructural rovibrational partition functions can introduce errors up to 75%.

Conclusions:

  • Conformational flexibility significantly influences the accuracy of theoretical rate constants.
  • Careful consideration of all relevant conformations is necessary for reliable computational predictions.
  • The MS-CVT/SCT method provides a robust framework for studying complex reaction systems.