Quantum mechanical and 13C dynamic NMR study of 1,3-dimethylthiourea conformational isomerizations

Candee C. Chambers, Edet F. Archibong, Ali Jabalameli, Richard H. Sullivan, David J. Giesen, Christopher J. Cramer, Donald G. Truhlar

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19 Scopus citations

Abstract

We present 13C dynamic NMR results for relative free energies of equilibrium structures and free energies of activation for conformational transformations of 1,3-dimethylthiourea in aqueous solution, and we compare the results to theoretical predictions. The latter are based on ab initio gas-phase electronic structure calculations of the geometries, dipole moments, and energies combined with semiempirical molecular orbital calculations of the free energies of solvation in three different solvents. The gas-phase electronic structure calculations were performed using Møller-Plesset second-order (MP2) perturbation theory with a correlation-consistent polarized valence-double-zeta basis set; we calculated relative energies for the three minima Z, Z, E,Z, and E,E and for three transition states on the potential energy surface. The solvation energy calculations were carried out using the SM5.4/AMI-aqueous, -chloroform, and -organic solvation models; these solvation models are based on semiempirical molecular orbital theory with class-IV charges and geometry-based first-solvation-shell effects. The relative energies of the conformers and transition states are compared to experiment in water and five organic solvents.

Original languageEnglish (US)
Pages (from-to)61-68
Number of pages8
JournalJournal of Molecular Structure: THEOCHEM
Volume425
Issue number1-2
DOIs
StatePublished - Feb 19 1998

Bibliographical note

Funding Information:
The authors are grateful to G.D. Hawkins for assistance.D JG gratefully acknowledges as Kodak Graduate School Fellowship. This work was also supportedi n part by the National Science Foundation under grant no. CHE94-23927. This work was also sponsored in part by the Army High Performance Computing Research Center under the auspices of the Departmento f the Army, Army ResearchL abora-tory cooperative agreementn umber DAAH04-952-0003/contracnt umber DAAH04-95-C-0008. The content does not necessarily reflect the position or the policy of the government,a nd no official endorsement should be inferred.

Keywords

  • Conformational analysis
  • Free energy of activation
  • Isomerization
  • Solvation
  • Thiourea

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