期刊
CHEMPHYSCHEM
卷 20, 期 23, 页码 3238-3244出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.201900811
关键词
Dissociation Energy; Hydrogen Bonding; Infrared Synchrotron Radiation; Non-Covalent Forces; Vibrational Zero-Point Energy
资金
- CALIPSOplus project - European Union's Horizon 2020 Research and Innovation programme
The high-resolution infrared absorption spectrum of the donor bending fundamental band nu 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 nu 61 transition has the typical appearance of a perpendicular type band associated with a sigma-pi 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 nu(0) 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 D-0 of this prototypical homodimer.
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