The infrared spectrum of the nitric oxide dimer cation: Problems for density functional theory and a muddled relationship to experiment
- Department of Chemistry, Beijing Normal University, Beijing 100857, Peoples Republic of (China)
- Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602 (United States)
- Department of Chemistry, Beijing Normal University, Beijing 100875, Peoples Republic of (China)
{ital Ab initio} and density functional theory (DFT) methods have been used to study the geometries, vibrational frequencies, and infrared intensities for the trans-, cis-, and gauche-structures of the ONNO{sup +} cation. Five different functionals were employed for comparison. Double-{zeta} plus polarization (DZP) basis sets and triple-{zeta} plus double polarization with {ital f} functions (TZ2Pf) basis sets were utilized. The ground state of the trans-ONNO cation is of {sup 2}A{sub g} symmetry. The prominent infrared absorption is predicted as {approximately}1900 cm{sup {minus}1} based upon the DFT methods. However, this DFT prediction is suspect since ONNO{sup +} exhibits inverse symmetry breaking, dissociating to the physically absurd limit ON{sup +1/2} plus NO{sup +1/2}. This inverse symmetry breaking phenomenon was discussed in an important 1997 paper by Bally and Sastry [J. Phys. Chem. A {bold 101}, 7923 (1997)]. Therefore, a higher theoretical level, Brueckner coupled-cluster method was ultimately applied, and the harmonic vibrational frequency of this mode was predicted to be about 1550{endash}1650 cm{sup {minus}1}. The important matrix isolation infrared experiments of Jacox {ital et al.} [J. Chem. Phys. {bold 93}, 7609 (1990)], Lugez {ital et al.} [J. Chem. Phys. {bold 110}, 10345 (1999)], Hacaloglu {ital et al.} [J. Phys. Chem. {bold 94}, 1759 (1990)], Andrews {ital et al.} [J. Phys. Chem. A {bold 103}, 4167 (1999)], and Strobel {ital et al.} [J. Phys. Chem. {bold 99}, 872 (1995)] are carefully considered. {copyright} {ital 1999 American Institute of Physics.}
- OSTI ID:
- 355435
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 6 Vol. 111; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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