Abstract
The new compound H3PAgI has been synthesized in the gas phase by means of the reaction of laser-ablated silver metal with a pulse of gas consisting of a dilute mixture of ICF3 and PH3 in argon. Ground-state rotational spectra were detected and assigned for the two isotopologues H3P(107)AgI and H3P(109)AgI in their natural abundance by means of a chirped-pulse, Fourier-transform, microwave spectrometer. Both isotopologues exhibit rotational spectra of the symmetric-top type, analysis of which led to accurate values of the rotational constant B0, the quartic centrifugal distortion constants DJ and DJK, and the iodine nuclear quadrupole coupling constant χaa(I) = eQqaa. Ab initio calculations at the explicitly-correlated level of theory CCSD(T)(F12*)/aug-cc-pVDZ confirmed that the atoms PAg-I lie on the C3 axis in that order. The experimental rotational constants were interpreted to give the bond lengths r0(PAg) = 2.3488(20) Å and r0(Ag-I) = 2.5483(1) Å, in good agreement with the equilibrium lengths of 2.3387 Å and 2.5537 Å, respectively, obtained in the ab initio calculations. Measures of the strength of the interaction of PH3 and AgI (the dissociation energy De for the process H3PAgI = H3P + AgI and the intermolecular stretching force constant FPAg) are presented and are interpreted to show that the order of binding strength is H3PHI < H3PICl < H3PAgI for these metal-bonded molecules and their halogen-bonded and hydrogen-bonded analogues.
Highlights
The new compound H3PÁ Á ÁAgI has been synthesized in the gas phase by means of the reaction of laserablated silver metal with a pulse of gas consisting of a dilute mixture of ICF3 and PH3 in argon
Several molecules H3NÁ Á ÁMX, where M = Cu or Ag and X = F, Cl or I, have been detected and characterised recently in the gas phase for the first time through their rotational spectra,[17,18,19] H3NÁ Á ÁCuCl was identified in the solid state earlier.[20]
We report here the rotational spectrum of H3PÁ Á ÁAg–I and some of its properties derived therefrom
Summary
The rotational spectrum, namely the angular geometry, the distances r(BÁ Á ÁM) and r(M–X), the strength of the intermolecular bond BÁ Á ÁM, and the electric charge redistribution that accompanies formation of BÁ Á ÁMX. The theoretical component of the investigations involves ab initio calculations at the CCSD(T)(F12*) explicitly correlated level of theory, usually with the largest basis set affordable These calculations have the advantage of providing accurate properties of the isolated molecule, which can be compared with the experimental results. Our interest here is to examine the geometry and binding strength of H3PÁ Á ÁAg–I and the electric charge redistribution within Ag–I that accompanies its formation These properties will be compared with those of the closely related molecule H3NÁ Á ÁCuI,[19] with those of their hydrogen-bonded analogues H3PÁ Á ÁHI25 and H3NÁ Á ÁHI26 and with those of their halogen-bonded relatives, H3PÁ Á ÁICl27 and H3NÁ Á ÁICl.[28]
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