Sequential bond dissociation energies of (Th(CO)x)+,x = 1-6: Quantum computational studies alternative approach. The capabilities of mass-spectrometry in the determination of molecule geometry

Abstract

The calculation problem of bond-dissociation energy BDE((CO)x-1Th+-CO), x = 1-6 was solved using the fundamental law of nature determining the dependence of chemical bond dissociation energy on its length. The recommended experimental values from literature are as follows bond dissociation energies BDE(Th+-CO)= 0.940.06 eV, BDE((CO)Th+-CO)=1.050.09 eV, BDE((CO)2Th+-CO)=1.090.05 eV, BDE((CO)3Th+-CO)=0.820.07 eV, BDE((CO)4Th+-CO)=0.630.05 eV, BDE((CO)5Th+-CO)=0.700.05 eV. The theoretical data calculated in this article are 0.934 eV, 1.056 eV, 1.082 eV, 0.82 eV, 0.634 eV, 0.708 eV correspondingly which is in good agreement with the literature. For the first time it was shown that experimental values of bond-dissociation energies, obtained with mass-spectrometry, can be successfully utilized in the calculations of the geometrical properties of molecules. The carried out calculations for thorium hexacarbonyl cation Th(CO)6+ determine its structure as tetragonal bipyramid. The found bond length values r((CO)x-1 Th+-CO) are 2.414 A and 2.444 A for equatorial and axial bonds correspondingly