Origin of the solvent effects on the barrier to amide isomerization from the combined QM/MM Monte Carlo simulations

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Abstract

The origin of the solvent effects on the free energy of activation for the isomerization of N,N-dimethylformamide in water, CHCl3 and CCl4 has been investigated through statistical mechanical simulations using the combined quantum mechanical and molecular mechanical AM1/OPLS potential. The differential solvations between the ground state and transition state in various solvents can be attributed to the differences in molecular dipole moments in solution, and to the solvent polarization effects. In polar solvents, DMF is polarized more favorably in the ground state than in the rotated conformers, leading to greater solvent contributions. The modest solvent effects in CCl4 are a reflection of its much smaller dielectric constant.

Original languageEnglish (US)
Pages (from-to)507-519
Number of pages13
JournalProceedings of the Indian Academy of Sciences - Chemical Sciences
Volume106
Issue number2
DOIs
StatePublished - Apr 1994

Keywords

  • Amide isomerization
  • combined QM/MM Monte Carlo simulations
  • polarization effects
  • solvent effects

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