The Application of Electrospray Mass Spectrometry to Solution Speciation: An Integrated Experimental and Computational Approach

Abstract

Electrospray ionization mass spectrometry (ESI-MS) is a promising technique for the study of metal:ligand solution speciation. While ESI-MS is frequently used qualitatively with some success, quantitative use of the technique has been held back by observed deviations between the gas phase measurements and known solution speciation. This work explores three significant causes of this observed deviation: new solution equilibria formed within evaporating droplets, differing ionization efficiencies of analyte species, and the inclusion of organic cosolvents such as methanol to enhance ionization efficiency.