Sodium Coordination and Protonation of Poly(ethoxy phosphate) Chains in the Gas Phase Probed by Ion Mobility-Mass...

The two-dimensional shape information yielded by ion mobility-mass spectrometry (IM-MS), usually reported as collision cross section (CCS), is often correlated to the underlying three-dimensional structures of the ions through computational chemistry. Here, we used theoretical approaches based on molecular mechanics (MM), molecular dynamics (MD), and density functional theory (DFT) to elucidate the structures of sodiated poly(ethoxy phosphate) polymer ions at different degrees of polymerization (DP) for three different charge states (1+, 2+, and 3+) by comparing computational results to experimentally obtained CCS values. From the calculated structures, we extract several key interaction distances which merge in clusters for all screened charge states and DPs, independent of the three-dimensional structures and the polymer ion structural rearrangements. These distances were also used to extract the minimum coordination numbers in poly(ethoxy phosphate) and to describe the preferred coordination geometries. When sodiated and protonated polymer ions are compared, the experimental CCS evolutions differ at small DP values and merge at higher DPs. We investigated in more depth this difference for two selected species, namely, [PEtP₅ + 2Na⁺]²⁺ and [PEtP₅ + 2H⁺]²⁺. For the protonated ions, we explored the different protonation sites to extract three-dimensional structure candidates and rationalize the CCS behaviors.