Abstract
First-principles calculations are performed to characterize the NO adsorption on large carbonaceous clusters modeling the surface of soot. Adsorption on the face and on the edges of perfect and defective clusters is considered in the calculations. It is shown that the first situation corresponds to physisorption and requires taking into account long-range dispersion interactions in the calculations. In contrast, interaction of NO with the unsaturated edge of a defective cluster leads preferentially to a C-N rather than to a C-O chemical binding. This indicates that soot may be an efficient sink for NO in the troposphere only if it contains a high number of unsaturated carbon atoms. From a more fundamental point of view, this study also clearly evidences that quantum calculations have to be carefully conducted when considering the interaction between radical species and carbonaceous surfaces. Problems encountered with the choice of the functional used in density functional theory approaches as well as with the size of the basis set, spin multiplicity, and spin contamination have to be systematically addressed before any relevant conclusion can be drawn.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.