## Abstract

An accurate near-equilibrium potential energy surface (PES) has been constructed for the azide ion (N3^{-}) on the basis of coupled cluster calculations up to CCSDTQ (Kállay, M.; Surján, P. R. J. Chem. Phys. 2001, 115, 2945.), with contributions from inner-shell correlation and special relativity being taken into account as well. A larger number of rovibrational states has been investigated by variational calculations with Watson's isomorphic Hamiltonian for linear molecules. Analogous calculations for CO_{2} demonstrate the high quality of this type of calculations. The G_{v} values of the symmetric stretching and bending vibration of ^{14}N3^{-} are predicted to be ν_{1} = 1307.9 cm^{-1} and ν_{2} = 629.3 cm^{-1}, with an uncertainty of ca. 1 cm^{-1}. Fermi resonance is less pronounced for the lower polyads of ^{14}N3^{-} compared with ^{12}C ^{16}O_{2} but is as strong as in CO_{2} for the lowest diad of isotopologue 15-14-15. The band origin of the antisymmetric stretching vibration of ^{14}N3^{-} is calculated to be ν_{3} = 1986.4 cm^{-1}, only 0.1 cm^{-1} lower than the experimental value. The corresponding vibrational transition dipole moment is predicted to be as large as μ = 0.476 D, 46% higher than calculated for CO_{2}. The perturbed combination tone (01^{1}1), which was accessible through diode laser IR spectroscopy, undergoes anharmonic interaction with at least two other vibrational states.

Originalsprache | Englisch |
---|---|

Seiten (von - bis) | 13806-13814 |

Seitenumfang | 9 |

Fachzeitschrift | Journal of Physical Chemistry A |

Jahrgang | 117 |

Ausgabenummer | 50 |

DOIs | |

Publikationsstatus | Veröffentlicht - 19 Dez. 2013 |

Extern publiziert | Ja |

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