Energetics and vibrational analysis of methyl salicylate isomers.
Energetics and vibrational analysis study of six isomers of methyl salicylate in their singlet ground state and first excited triple state is put forward in this work at the density functional theory level and large basis sets. The ketoB isomer is the lowest energy isomer, followed by its rotamer ketoA. For both ketoB and ketoA their enolized tautomers are found to be stable as well as their open forms that lack the internal hydrogen bond. The calculated vibrational spectra are in excellent agreement with IR experiments of methyl salicylate in the vapor phase. It is demonstrated that solvent effects have a weak influence on the stability of these isomers. The ionization reaction from ketoB to ketoA shows a high barrier of 0.67 eV ensuring that thermal and chemical equilibria yield systems containing mostly the ketoB isomer at normal conditions.
Massaro
Richard D
RD
Computational Materials Science Center and Department of Computational and Data Sciences, George Mason University, Fairfax, Virginia 22030, USA.
Dai
Yafei
Y
Blaisten-Barojas
Estela
E
D003198:Computer Simulation; D007536:Isomerism; D008956:Models, Chemical; D012459:Salicylates / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013816:Thermodynamics; D014732:Vibration
D012459:Salicylates; C033069:methyl salicylate