Hydrogen-bonding-induced enhancement of Fermi resonances: a linear IR and nonlinear 2D-IR study of aniline-d5

J Phys Chem B. 2013 Dec 12;117(49):15843-55. doi: 10.1021/jp4084103. Epub 2013 Oct 1.

Abstract

Hydrogen bonding of the amino group of aniline-d5 results in a huge enhancement of the NH2 bending overtone absorption strength, mainly attributed to the Fermi resonance effect. A quantitative analysis is presented, using a hybrid mode representation and encompassing experimental data on aniline with 0, 1, or 2 hydrogen bonds to dimethylsulfoxide (DMSO). Changes in enthalpy, hydrogen-bonding-induced frequency shifts, and the transition dipole moment increase of the local N-H stretching oscillator all demonstrate that the hydrogen bond is strongest in the single hydrogen-bonded complex. Linear IR overtone spectra show that the oscillator strength decreases upon hydrogen bonding for the N-H stretching overtones, which is opposite to the effect on the fundamental N-H stretching transitions. Polarization resolved 2D-IR spectra provide detailed information on the N-H stretching overtone manifold and support the relative orientations of the various IR transitions.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Aniline Compounds / chemistry*
  • Dimethyl Sulfoxide / chemistry
  • Hydrogen Bonding
  • Kinetics
  • Spectrophotometry, Infrared*

Substances

  • Aniline Compounds
  • aniline
  • Dimethyl Sulfoxide