Molecular Dynamics Study of the Tautomeric Equilibrium in the 4-Nitro- and 2,4, 6-Trichloro Derivatives of 2-(N, N -Dialkyloaminomethyl)phenol

Details

• Personal Author:
  Fedorowicz A ; Koll A ; Mavri J
• Description:
  Molecular dynamics thermodynamic integration (MDTI) method and quantum chemical calculations at the density functional theory B3LYP 6-31+(d,p) level, which included the Tomasi model of the solvent reaction field, were applied to study the tautomeric equilibrium of Mannich base in methanol solution. The values obtained for the free-energy difference are in good agreement with experimental data. However, the results from quantum mechanical calculations were not as good as the results of MDTI simulations owing to inappropriate treatment of intermolecular hydrogen bonds between the solute molecule and the first shell of solvent molecules in the Tomasi model of the solvent reaction field. The radial distribution functions between solute atoms and solvent atoms confirmed the formation of hydrogen bonds between the solute molecule and surrounding methanol molecules and indicated that the zwitterionic form is associated more with an organized solvent structure at the level of the first solvation shell than is the molecular form. [Description provided by NIOSH]
• Subjects:
  Coal Coal Mining Geology Mining Occupational Health Safety
• Keywords:
  Chemical-binding Chemical-properties Molecular-biology Solvents Thermodynamic-reactions Thermodynamics
• ISSN:
  1432-881X
• Document Type:
  Text
• Genre:
  Journal Article
• Place as Subject:
  Michigan ; North Carolina ; OSHA Region 10 ; OSHA Region 3 ; OSHA Region 4 ; OSHA Region 5 ; Washington ; West Virginia
• CIO:
  National Institute for Occupational Safety and Health (NIOSH)
• Division:
  HELD - Health Effects Laboratory Division
• Topic:
  Workplace Safety & Health
• Location:
  North America
• Pages in Document:
  220-228
• Volume:
  109
• Issue:
  4
• NIOSHTIC Number:
  nn:20033267
• Citation:
  Theor Chem Acc 2003 May; 109(4):220-228
• Contact Point Address:
  A. Fedorowicz, National Institute for Occupational Safety and Health, 1095 Willowdale Road, Morgantown, WV 26505
• Federal Fiscal Year:
  2003
• Peer Reviewed:
  True
• Source Full Name:
  Theoretical Chemistry Accounts
• Collection(s):
  National Institute for Occupational Safety and Health
• Main Document Checksum:
  urn:sha-512:42de18dd7e4c101cfb83a318aaa0b13aa5dcbd80a5713390f15e8b5f2214afd03d50b08aa8dfb6bd99c7c3b695f77c1caab233658047070f2ac4cd51aac04863
• Download URL:
  https://stacks.cdc.gov/view/cdc/188915/cdc_188915_DS1.pdf
• File Type:
  [PDF - 1.01 MB ]