Study of the interaction between water and hydrogen sulfide with polycyclic aromatic hydrocarbons.
A computational study has been carried out for determining the characteristics of the interaction between one water and hydrogen sulfide molecule with a series of polycyclic aromatic hydrocarbons of increasing size, namely, benzene, anthracene, triphenylene, coronene, circumcoronene, and dicircumcoronene. Potential energy curves were calculated for structures where H(2)X (X=O,S) molecule is located over the central six-membered ring with its hydrogen atoms pointing toward to (mode A) or away from (mode B) the hydrocarbon. The accuracy of different methods has been tested against the results of coupled cluster calculations extrapolated to basis set limit for the smaller hydrocarbons. The spin component scaled MP2 (SCS-MP2) method and a density functional theory method empirically corrected for dispersion (DFT-D) reproduce fairly well the results of high level calculations and therefore were employed for studying the larger systems, though DFT-D seems to underestimate the interaction in hydrogen sulfide clusters. Water complexes in mode A have interaction energies that hardly change with the size of the hydrocarbon due to compensation between the increase in the correlation contribution to the interaction energy and the increase in the repulsive character of the Hartree-Fock energy. For all the other clusters studied, there is a continuous increase in the intensity of the interaction as the size of the hydrocarbon increases, suggesting already converged values for circumcoronene. The interaction energy for water clusters extrapolated to an infinite number of carbon atoms amounts to -13.0 and -15.8 kJ/mol with SCS-MP2 and DFT-D, respectively. Hydrogen sulfide interacts more strongly than water with the hydrocarbons studied, leading to a limiting value of -21.7 kJ/mol with the SCS-MP2 method. Also, complexes in mode B are less stable than the corresponding A structures, with interaction energies amounting to -8.2 and -18.2 kJ/mol for water and hydrogen sulfide, respectively. The DFT-D calculations give values of -16.2 and -9.3 kJ/mol for hydrogen sulfide complexes in modes A and B, less negative than those predicted by the SCS-MP2 method, probably indicating problems with sulfur dispersion parameters.
Cabaleiro-Lago
Enrique M
EM
Departamento de Química Física, Facultade de Ciencias, Universidade de Santiago de Compostela, Campus de Lugo, Avda. Alfonso X El Sabio s/n, 27002 Lugo, Galicia, Spain. caba.lago@usc.es
Carrazana-García
Jorge A
JA
Rodríguez-Otero
Jesús
J
D003198:Computer Simulation; D006862:Hydrogen Sulfide / Q000737:chemistry*; D008956:Models, Chemical; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
D011084:Polycyclic Aromatic Hydrocarbons; D014867:Water; D006862:Hydrogen Sulfide