caa a22 4500 605512906 CHVBK 20210128100657.0 cr unu---uuuuu 210128e20150801xx s 000 0 eng 10.1007/s00894-015-2769-z doi (NATIONALLICENCE)springer-10.1007/s00894-015-2769-z The solvatochromism of phenolate betaines: comparing different cavities of a polarized continuum model [Elektronische Daten] [Marcos Rezende, Moisés Domínguez] Two variations of the polarized continuum model employing default ("PCM model”) and SMD radii ("SMD model”) were compared for the reproduction of the solvatochromic behavior of Reichardt's betaine dye, and of eight other phenolate betaines that exhibit a negative, positive or an inverted solvatochromic behavior. Molecules were optimized at the CAM B3LYP/6-31+G(d,p) level of theory, and transition energies were calculated with the TD-DFT method. The PCM model failed to reproduce the negative and the inverted solvachromism of these dyes in protic solvents. The SMD model, though not entirely accounting for hydrogen-bond effects in small, polar hydroxylic solvents, should be recommended as a better alternative for the theoretical simulation of the solvatochromism of phenolate betaines in medium to highly polar solvents. Graphical Abstract A comparison of two polarized continuum models ("default PCM” and "PCM/SMD”) for reproducing the solvatochromism of phenolate betaines, with nine examples of negative, positive, and inverted behavior Springer-Verlag Berlin Heidelberg, 2015 Phenolate betaines nationallicence Polarized continuum model (PCM) nationallicence Positive, negative and reverse solvatochromism nationallicence Universal solvation model (SMD) nationallicence Rezende Marcos Facultad de Química y Biología, Universidad de Santiago, Av. B.O'Higgins 3363, Santiago, Chile aut Domínguez Moisés Facultad de Química y Biología, Universidad de Santiago, Av. B.O'Higgins 3363, Santiago, Chile aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/8(2015-08-01), 1-11 1610-2940 21:8<1 2015 21 894 https://doi.org/10.1007/s00894-015-2769-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/s00894-015-2769-z text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Rezende Marcos Facultad de Química y Biología, Universidad de Santiago, Av. B.O'Higgins 3363, Santiago, Chile aut NATIONALLICENCE 700 1- Domínguez Moisés Facultad de Química y Biología, Universidad de Santiago, Av. B.O'Higgins 3363, Santiago, Chile aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/8(2015-08-01), 1-11 1610-2940 21:8<1 2015 21 894