Ion-neutral clustering alters gas-phase hydrogen-deuterium exchange rates

The rates and mechanisms of chemical reactions that occur at a phase boundary often differ considerably from chemical behavior in bulk solution, but remain difficult to quantify. Ion-neutral interactions are one such class of chemical reactions whose behavior during the nascent stages of solvation differs from bulk solution while occupying critical roles in aerosol formation, atmospheric chemistry, and gas-phase ion separations. Through a gas-phase ion separation technique utilizing a counter-current flow of deuterated vapor, we quantify the degree of hydrogen-deuterium exchange (HDX) and ion-neutral clustering on a series of model chemical systems (i.e. amino acids). By simultaneously quantifying the degree of vapor association and HDX, the effects of cluster formation on reaction kinetics are realized. These results imply that cluster formation cannot be ignored when modeling complex nucleation processes and biopolymer structural dynamics.

Automated summary

The rates and mechanisms of chemical reactions at phase boundaries are different from those in bulk solution, but are difficult to quantify. Ion-neutral interactions play critical roles in aerosol formation, atmospheric chemistry, and gas-phase ion separations, and their behavior during the early stages of solvation differs from bulk solution. By quantifying the degree of hydrogen-deuterium exchange (HDX) and ion-neutral clustering through a gas-phase ion separation technique, we found that cluster formation cannot be ignored when modeling complex nucleation processes and biopolymer structural dynamics.