Physical chemistry chemical physics : PCCP

Solvent-assisted conformational isomerization and the conformationally-pure REMPI spectrum of 3-aminophenol.

PMID 21399792


3-Aminophenol (3AP) has two conformers, cis and trans, depending on the orientation of the OH group relative to the NH(2) group. While both conformers are found in the jet-cooled spectra of 3AP, only the trans isomer was found in the REMPI spectrum of the 3AP(NH(3))(1) cluster. It was suggested that the cis conformer of the cluster isomerizes to the more stable trans conformer in the ground state during supersonic expansion. Solvent-assisted conformational isomerization (SACI) is believed to drive the population into the more stable trans isomer. SACI also occurs for the 3AP monomer, reducing 50% of the cis/trans ratio when the ammonia concentration in the expansion is higher than 0.1%. Depending on the expansion condition, the cis conformer can be completely depleted. When other solvents were introduced in the expansion, SACI occurred with only certain solvents whose binding energy is higher than the isomerization barrier. SACI can be used as a means to prepare the most stable conformer of gas phase biomolecules.