## Abstract

Complexes of H_{3}N⋯CuF and H_{3}N⋯CuI have been synthesised in the gas phase and characterized by microwave spectroscopy. The rotational spectra of 4 isotopologues of H_{3}N⋯CuF and 5 isotopologues of H_{3}N⋯CuI have been measured in the 6.5-18.5 GHz frequency range using a chirped-pulse Fourier transform microwave spectrometer. Each complex is generated from a gas sample containing NH_{3} and a halogen-containing precursor diluted in Ar. Copper is introduced by laser ablation of a solid target prior to supersonic expansion of the sample into the vacuum chamber of the microwave spectrometer. The spectrum of each complex is characteristic of a symmetric rotor and a C_{3v} geometry in which the N, Cu and X atoms (where X is F or I) lie on the Ca3 axis. The rotational constant (B_{0}), centrifugal distortion constants (D_{J} and D_{JK}), nuclear spin-rotation (C_{bb}(Cu) = C_{cc}(Cu)) constant (for H_{3}N⋯CuF only) and nuclear quadrupole coupling constants (χ_{aa}(X) where (X = N, Cu, I)) are fitted to the observed transition frequencies. Structural parameters are determined from the measured rotational constants and also calculated ab initio at the CCSD(T)(F12∗)/AVQZ level of theory. Force constants describing the interaction between ammonia and each metal halide are determined from D_{J} for each complex. Trends in the interaction strengths and geometries of B⋯CuX (B = NH_{3}, CO) (X = F, Cl, Br, I) are discussed.

Original language | English |
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Pages (from-to) | 13638-13645 |

Number of pages | 8 |

Journal | Physical Chemistry Chemical Physics |

Volume | 18 |

Issue number | 19 |

Early online date | 19 Apr 2016 |

DOIs | |

Publication status | Published - 21 May 2016 |

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_{3}N⋯CuI studied by rotational spectroscopy and: Ab initio calculations: The effect of X (X = F, Cl, Br, I) in OC⋯CuX and H

_{3}N⋯CuX'. Together they form a unique fingerprint.