Dissociation of nitric acid at an aqueous surface: Large amplitude motions in the contact ion pair to solvent-separated ion pair conversion
Literature Information
Shuzhi Wang, Roberto Bianco
Beyond its fundamental interest, the acid dissociation of nitric acid (HNO3) at an aqueous interface is of importance in a wide variety of atmospheric contexts. Here we present a Car–Parrinello molecular dynamics (CPMD) study of the second step of this process, the formation, via proton transfer (PT), of a solvent-separated ion pair (SSIP) from a contact ion pair (CIP) of the hydronium (H3O+) and the nitrate (NO−3) ions. This reaction represents an extension of our earlier CPMD study of the first PT step to produce the CIP from molecular HNO3 at various locations at and below the aqueous surface (S. Wang, R. Bianco and J. T. Hynes, J. Phys. Chem. A, 2009, 113, 1295); it is important in establishing the ionic distribution in the aqueous interfacial region, with potential consequences for heterogeneous reactions occurring in that region. We focus on the large amplitude, microscopic level motions—such as the hydrogen-bonding coordination number changes around the proton-donating and -accepting species—which are key for the CIP → SSIP PT conversion.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.












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