Calculations and analysis of 55Mn nuclear quadrupole coupling for asymmetric top acyl methyl manganese pentacarbonyl

Abstract

Revised assignments of the measured transitions for the asymmetric top acyl isomers of methyl manganese pentacarbonyl are presented, along with a corresponding fit to determine rotational and quadrupole coupling constants. New assignments for measured transitions give a better fit to the spectrum and better agreement between experimental and calculated quadrupole coupling strengths. The best agreements were obtained for B3LYP and M11 DFT calculations with triple and quadruple-zeta basis sets. Experimental molecular parameters from the new analysis are: A = 840.0843(52), B = 774.2861(17), C = 625.6528(13). DJ = 0.000212(21). DJK = 0.00488(18), 1.5χaa = −46.96(11), 0.25(χbb - χcc) = -13.44(3) MHz.