HSO2+Formation from Ion-Molecule Reactions of SO2⋅+with Water and Methane: Two Fast Reactions with Reverse Temperature-Dependent Kinetic Trend.
In this work an experimental and theoretical study on the formation of HSO2+ion from the SO2⋅++CH4and SO2⋅++H2O ion-molecule reactions at different temperatures is reported. Tunable synchrotron radiation was used to produce the SO2⋅+ion in excited ro-vibrational levels of the ionic ground state X2A1and mass spectrometry was employed to identify the product ions. Calculations in the frame of the density functional theory and variational transition state theory were combined to explore the dynamics of the reactions. The experimental results show that HSO2+is the only product in both reactions. Its yield decreases monotonically with photon energy in the SO2⋅++H2O reaction, while it decreases at first and then increases in the SO2⋅++CH4reaction. Theory confirms this trend by calculating the rate constants at different temperatures and explains the results by means of the polar, spin and charge effects as well as structural reorganization occurring in the reaction coordinate. The dynamic behavior observed in these two reactions is of general and fundamental interest. It can also provide some insights on the role of these reactions in astrochemistry as well as in their use as models for bond-activation reactions.
Dipartimento di Chimica, Sapienza Università di Roma, Pl.e Aldo Moro 5, 00185, Roma, Italy.|Istituto di Struttura della Materia (ISM), Consiglio Nazionale delle Ricerche (CNR), Area della Ricerca di Roma 1, via Salaria Km 29,300, Monterotondo Scalo (RM), 00016, Italy.
Antonella
A
Cartoni
Istituto di Struttura della Materia (ISM), Consiglio Nazionale delle Ricerche (CNR), Area della Ricerca di Roma 2, via del Fosso del Cavaliere 10, 00133, Roma, Italy.
Daniele
D
Catone
Istituto di Struttura della Materia (ISM), Consiglio Nazionale delle Ricerche (CNR), Area della Ricerca di Roma 1, via Salaria Km 29,300, Monterotondo Scalo (RM), 00016, Italy.
Paola
P
Bolognesi
Istituto per lo Studio dei Materiali Nanostrutturati (ISMN), Dipartimento di Chimica, Sapienza Università di Roma, P.le Aldo Moro 5, 00185, Roma, Italy.
Mauro
M
Satta
Istituto di Struttura della Materia (ISM), Consiglio Nazionale delle Ricerche (CNR), Area della Ricerca di Roma 1, via Salaria Km 29,300, Monterotondo Scalo (RM), 00016, Italy.
Pal
P
Markus
Istituto di Struttura della Materia (ISM), Consiglio Nazionale delle Ricerche (CNR), Area della Ricerca di Roma 1, via Salaria Km 29,300, Monterotondo Scalo (RM), 00016, Italy.
Lorenzo
L
Avaldi
computational chemistry; kinetics; rate constants; sulfur dioxide; synchrotron radiation