(CH3)3N···AgI and H3N···AgI studied by broadband rotational spectroscopy and ab initio calculations

Abstract

The pure rotational spectra of 8 isotopologues of H$_{3}$N$cdot$$cdot$$cdot$AgI and 6 isotopologues of (C{H$_{3}$})$_{3}$N$cdot$$cdot$$cdot$AgI were measured in a chirped pulse Fourier-transform microwave spectrometer. The complexes were synthesized in a molecular beam from a gas sample containing H$_{3}$N or (C{H$_{3}$})$_{3}$N and CF$_{3}$I precursors diluted in argon. Laser ablation was used to introduce silver atoms to the gas phase. The rotational constant textit{B}$_{0}$, centrifugal distortion constants textit{D}$_{J}$ and textit{D}$_{JK}$, and the nuclear quadrupole coupling constant $chi$$_{aa}$(I) have been determined for (C{H$_{3}$})$_{3}$$^{14/15}$N$cdot$$cdot$$cdot$$^{107/109}$AgI, (C{D$_{3}$})$_{3}$N$cdot$$cdot$$cdot$$^{107/109}$AgI, H$_{3}$$^{14/15}$N$cdot$$cdot$$cdot$$^{107/109}$AgI and D$_{3}$N$cdot$$cdot$$cdot$$^{107/109}$AgI by fitting the measured transitions to a symmetric top Hamiltonian. The spectroscopic constants (textit{B}$_{0}$+ textit{C}$_{0}$), $Delta$$_{J}$ and $chi$$_{aa}$(I) have been determined for D$_{2}$HN$cdot$$cdot$$cdot$$^{107/109}$AgI through fits that employed a Hamiltonian appropriate for a very near prolate asymmetric rotor. Partial effective (textit{r}$_{0}$) and substitution (textit{r}$_{s}$) structures have been determined