caa a22 4500 60548757X CHVBK 20210128100451.0 cr unu---uuuuu 210128e20151201xx s 000 0 eng 10.1007/s00214-015-1732-5 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1732-5 Aggregation of photosensitizers: the role of dispersion and solvation on dimer formation energetics [Elektronische Daten] [Fernanda Bettanin, Tancredo de Carvalho Fontinelles, Cleiton Maciel, Luís Dias, Mauricio Coutinho-Neto, Paula Homem-de-Mello] A detailed account for the dimer formation energetics is computed for two commonly used photosensitizers: metal-free phthalocyanine (Pc) and methylene blue (MB), a cationic phenothiazine. Gas-phase calculations were performed using the density functional theory augmented with dispersion corrections using both the dispersion-correcting atom-centred potentials and the D2/D3 methods. SCS-MP2/CBS results were also provided for comparison. Hydration free energies were determined using continuum methodologies: namely the conductor-like polarizable continuum model, the solvation model density and a reparametrized version of the polarizable continuum model. For methylene blue, the Langevin dipole model was also used. Our results showed that the nature of aggregation is remarkably different for these two molecules, being dispersion driven for Pc while solvent driven for MB. For water and ethanol our results are in good agreement with the experimental data available for MB. We also provide quantitative estimates to the popular explanation put out by Mukerjee and Ghosh more than 40years ago that aggregation arises from solvent entropic and inter-species enthalpic contributions. Springer-Verlag Berlin Heidelberg, 2015 Phenothiazine nationallicence Phthalocyanine nationallicence Aggregation nationallicence π -Stacking nationallicence Dispersion interactions nationallicence Solvation effects nationallicence Bettanin Fernanda ABCSim, Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Av. dos Estados, 5001, 09210-580, Santo André, SP, Brazil aut de Carvalho Fontinelles Tancredo ABCSim, Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Av. dos Estados, 5001, 09210-580, Santo André, SP, Brazil aut Maciel Cleiton ABCSim, Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Av. dos Estados, 5001, 09210-580, Santo André, SP, Brazil aut Dias Luís Departamento de Química, FFCLRP, Universidade de São Paulo, Av. Bandeirantes, 3900, 14040-901, Ribeirão Preto, SP, Brazil aut Coutinho-Neto Mauricio ABCSim, Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Av. dos Estados, 5001, 09210-580, Santo André, SP, Brazil aut Homem-de-Mello Paula ABCSim, Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Av. dos Estados, 5001, 09210-580, Santo André, SP, Brazil aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/12(2015-12-01), 1-11 1432-881X 134:12<1 2015 134 214 https://doi.org/10.1007/s00214-015-1732-5 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/s00214-015-1732-5 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Bettanin Fernanda ABCSim, Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Av. dos Estados, 5001, 09210-580, Santo André, SP, Brazil aut NATIONALLICENCE 700 1- de Carvalho Fontinelles Tancredo ABCSim, Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Av. dos Estados, 5001, 09210-580, Santo André, SP, Brazil aut NATIONALLICENCE 700 1- Maciel Cleiton ABCSim, Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Av. dos Estados, 5001, 09210-580, Santo André, SP, Brazil aut NATIONALLICENCE 700 1- Dias Luís Departamento de Química, FFCLRP, Universidade de São Paulo, Av. Bandeirantes, 3900, 14040-901, Ribeirão Preto, SP, Brazil aut NATIONALLICENCE 700 1- Coutinho-Neto Mauricio ABCSim, Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Av. dos Estados, 5001, 09210-580, Santo André, SP, Brazil aut NATIONALLICENCE 700 1- Homem-de-Mello Paula ABCSim, Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Av. dos Estados, 5001, 09210-580, Santo André, SP, Brazil aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/12(2015-12-01), 1-11 1432-881X 134:12<1 2015 134 214