caa a22 4500 605488525 CHVBK 20210128100455.0 cr unu---uuuuu 210128e20150201xx s 000 0 eng 10.1007/s00214-014-1609-z doi (NATIONALLICENCE)springer-10.1007/s00214-014-1609-z Solvation effects on electronic polarization and reactivity indices at the air-water interface: insights from a theoretical study of cyanophenols [Elektronische Daten] [Marilia Martins-Costa, Manuel Ruiz-Lopez] We report a theoretical analysis of solvation effects on the molecular properties of ortho, meta, and para cyanophenol isomers at the air-water interface. The study was carried out using a self-consistent image charge polarizable continuum model, which allows to get clear insights on the solvation process and to rationalize the calculated differences with respect to solvation in bulk water. The results show that polarization at the air-water interface cannot be compared to polarization in a bulk solvent of low or medium polarity, as sometimes claimed. Indeed, though the calculated induced dipole moments at the interface are always significantly smaller than the induced moments in bulk water, other reactivity indices such as the chemical potential experience the largest solvation effects at the interface. Moreover, the relationship between solvation energies and solute polarity at the interface is not as simple as in the case of bulk solvation. In this respect, the study emphasizes the key role of the topology of the electrostatic field created by the polarized medium because its high anisotropy at the interface makes the molecular properties to be very dependent on the relative orientation of the solute. These findings can explain the higher chemical and photochemical reactivity previously described for some molecules and radicals of atmospheric interest. Springer-Verlag Berlin Heidelberg, 2015 Aqueous interfaces nationallicence Solvation effects nationallicence Reactivity indices nationallicence Electronic polarization nationallicence Dielectric model nationallicence Cyanophenol nationallicence Martins-Costa Marilia SRSMC, University of Lorraine, BP 70239, 54506, Vandoeuvre-les-Nancy, France aut Ruiz-Lopez Manuel SRSMC, University of Lorraine, BP 70239, 54506, Vandoeuvre-les-Nancy, France aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/2(2015-02-01), 1-7 1432-881X 134:2<1 2015 134 214 https://doi.org/10.1007/s00214-014-1609-z text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-014-1609-z text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Martins-Costa Marilia SRSMC, University of Lorraine, BP 70239, 54506, Vandoeuvre-les-Nancy, France aut NATIONALLICENCE 700 1- Ruiz-Lopez Manuel SRSMC, University of Lorraine, BP 70239, 54506, Vandoeuvre-les-Nancy, France aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/2(2015-02-01), 1-7 1432-881X 134:2<1 2015 134 214