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Does HNO 3 dissociate on gas-phase ice nanoparticles?

Anastasiya KhramchenkovaAndriy PysanenkoJozef ĎuranaBarbora KocábkováMichal FárníkJozef Lengyel
Published in: Physical chemistry chemical physics : PCCP (2023)
We investigated the dissociation of nitric acid on large water clusters (H 2 O) N , N̄ ≈ 30-500, i.e. , ice nanoparticles with diameters of 1-3 nm, in a molecular beam. The (H 2 O) N clusters were doped with single HNO 3 molecules in a pickup cell and probed by mass spectrometry after a low-energy (1.5-15 eV) electron attachment. The negative ion mass spectra provided direct evidence for HNO 3 dissociation with the formation of NO 3 - ⋯H 3 O + ion pairs, but over half of the observed cluster ions originated from non-dissociated HNO 3 molecules. This behavior is in contrast with the complete dissociation of nitric acid on amorphous ice surfaces above 100 K. Thus, the proton transfer is significantly suppressed on nanometer-sized particles compared to macroscopic ice surfaces. This can have considerable implications for heterogeneous processes on atmospheric ice particles.
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