Hydrogen-bonded acetic acid dimers: Anharmonic coupling and linear infrared spectra studied with density-functional theory

Anharmonic vibrational force field calculations provide a quantitative understanding of the width and substructure of the linear IR-absorption spectrum of the O-H stretching mode in acetic acid dimers (CH3-COOH)(2) and (CD3-COOH)(2). Anharmonic coupling of the high-frequency v(OH) mode to fingerprint and low-frequency modes is included resulting in 11- and 9-dimensional vibrational Hamiltonians. A sixth-order force field covering up to three-body interactions is used. Force constants are calculated by fitting one-dimensional potential-energy surfaces and a finite difference procedure applying density-functional theory [Becke 3 Lee-Yang-Parr 6-311+G(d,p)]. It is demonstrated that both anharmonic coupling to low-frequency modes as well as Fermi resonance coupling with fingerprint modes are important mechanisms explaining the line shape of the O-H stretching IR-absorption band in acetic acid dimers. (c) 2005 American Institute of Physics.