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Author Calvo, F. ♦ Yurtsever, E.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ COMPUTERIZED SIMULATION ♦ HYDROGEN ♦ ISOTOPE EFFECTS ♦ MOLECULAR DYNAMICS METHOD ♦ PATH INTEGRALS ♦ POLYCYCLIC AROMATIC HYDROCARBONS ♦ SOLVATION ♦ SOLVENTS ♦ STRONG INTERACTIONS
Abstract This work theoretically examines the progressive coating of planar polycyclic aromatic hydrocarbon (PAH) molecules ranging from benzene to circumcoronene (C{sub 54}H{sub 18}) by para-hydrogen and ortho-deuterium. The coarse-grained Silvera-Goldman potential has been extended to model the interactions between hydrogen molecules and individual atoms of the PAH and parametrized against quantum chemical calculations for benzene-H{sub 2}. Path-integral molecular dynamics simulations at 2 K were performed for increasingly large amounts of hydrogen coating the PAH up to the first solvation shell and beyond. From the simulations, various properties were determined such as the size of the first shell and its thickness as well as the solvation energy. The degree of delocalization was notably quantified from an energy landscape perspective, by monitoring the fluctuations among inherent structures sampled by the trajectories. Our results generally demonstrate a high degree of localization owing to relatively strong interactions between hydrogen and the PAH, and qualitatively minor isotopic effects. In the limit of large hydrogen amounts, the shell size and solvation energy both follow approximate linear relations with the numbers of carbon and hydrogen in the PAH.
ISSN 00219606
Educational Use Research
Learning Resource Type Article
Publisher Date 2016-06-14
Publisher Place United States
Journal Journal of Chemical Physics
Volume Number 144
Issue Number 22


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