High-Resolution Infrared Synchrotron Investigation of (HCN)2 and a Semi-Experimental Determination of the Dissociation Energy D0

Abstract

The high-resolution infrared absorption spectrum of the donor bending fundamental band ν ${61}_{}^{}$ of the homodimer (HCN)₂ has been collected by long-path static gas-phase Fourier transform spectroscopy at 207 K employing the highly brilliant 2.75 GeV electron storage ring source at Synchrotron SOLEIL. The rovibrational structure of the ν ${61}_{}^{}$ transition has the typical appearance of a perpendicular type band associated with a Σ-Π transition for a linear polyatomic molecule. The total number of 100 assigned transitions are fitted employing a standard semi-rigid linear molecule Hamiltonian, providing the band origin ν₀ of 779.05182(50) cm^-1 together with spectroscopic parameters for the degenerate excited state. This band origin, blue-shifted by 67.15 cm^-1 relative to the HCN monomer, provides the final significant contribution to the change of intra-molecular vibrational zero-point energy upon HCN dimerization. The combination with the vibrational zero-point energy contribution determined recently for the class of large-amplitude inter-molecular fundamental transitions then enables a complete determination of the total change of vibrational zero-point energy of 3.35±0.30 kJ mol^-1 . The new spectroscopic findings together with previously reported benchmark CCSDT(Q)/CBS electronic energies [Hoobler et al. ChemPhysChem. 19, 3257-3265 (2018)] provide the best semi-experimental estimate of 16.48±0.30 kJ mol^-1 for the dissociation energy D₀ of this prototypical homodimer.

Keywords: Dissociation Energy; Hydrogen Bonding; Infrared Synchrotron Radiation; Non-Covalent Forces; Vibrational Zero-Point Energy.

Figure 1

Portion of the infrared absorbance spectrum of the homodimer (HCN)₂ showing the ν ${}_6^1$ band in the spectral region of the central Q‐branch. The numbered lines above the trace indicate the assigned J‐values for the individual rovibrational transitions (see the electronic supplemental material).