Acetic acid dimers in a nitrogen matrix: Observation of structures containing the higher-energy conformer

J Chem Phys. 2015 Sep 14;143(10):104307. doi: 10.1063/1.4929575.

Abstract

Acetic acid (AA) dimers are studied experimentally by infrared spectroscopy in a N2 matrix and theoretically at the MP2/6-311++G(2d,2p) level of approximation. This work is focused on the first preparation and characterization of structures containing the higher-energy (cis) conformer of AA. Nine trans-trans, fourteen trans-cis, and six cis-cis dimers are theoretically predicted. Five trans-trans and a number of trans-cis dimers are identified in the experiments, but no indication of cis-cis dimers is found. Two trans-trans dimers and the trans-cis dimers are reported for the first time. One trans-cis dimer is prepared by selective vibrational excitation of the structurally related trans-trans dimer, which converts one of the trans subunits to the cis form. Several trans-cis dimers are obtained by annealing of a matrix containing both trans and cis monomers of AA. Tunneling-induced conversion of the trans-cis dimers into trans-trans forms (including two new trans-trans forms) is observed at low temperatures.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acetic Acid / chemistry*
  • Dimerization
  • Hydrogen Bonding
  • Models, Chemical
  • Molecular Structure
  • Nitrogen / chemistry*
  • Quantum Theory
  • Spectroscopy, Fourier Transform Infrared
  • Temperature
  • Vibration

Substances

  • Nitrogen
  • Acetic Acid