High resolution jet-cooled infrared absorption spectra of the formic acid dimer: a reinvestigation of the C-O stretch region.

Abstract

The vibration-rotation-tunneling absorption spectra of the formic acid dimer (HCOOH)2 have been measured in the C-O stretch region at 1215-1240 cm(-1) using a rapid-scan tunable diode laser spectrometer in conjunction with a slit supersonic expansion. The ν5 fundamental band of the HCOOH monomer is identified and the perturbed band-center is 1220.83329(10) cm(-1). Three vibrational bands centered at 1219.71, 1225.35, and 1233.95 cm(-1) are assigned to the two combination bands and the ν22 fundamental band of (HCOOH)2 unambiguously. The transition frequencies of these three vibrational bands are fitted together using a standard Watson A-reduced Hamiltonian, yielding precise rotational and centrifugal distortion constants for each tunneling level in the ground and excited vibrational states. The fitting results of the vibrational band centered at 1225.35 cm(-1) are in good agreement with a previous high resolution study [M. Ortlieb and M. Havenith, J. Phys. Chem. A. 111, 7355 (2007)]. The tunneling splittings in the vibrationally excited states are -0.00304(16), -0.01023(11), and -0.00318(12) cm(-1), respectively, where the minus indicates that the upper tunneling component lies energetically below the lower tunneling component. A three-state deperturbation analysis using the Fermi coupling constants obtained from a previous vibrational analysis [F. Ito, Chem. Phys. Lett. 447, 202 (2007)] fails to get the normal order of the tunneling levels for all the three excited vibrational states simultaneously.