Journal ArticleDOI
Understanding the interplay between the solvent and nuclear rearrangements in the negative solvatochromism of a push–pull flexible quinolinium cation
Oliviero Cannelli,Tommaso Giovannini,Alberto Baiardi,Benedetta Carlotti,Fausto Elisei,Chiara Cappelli +5 more
TLDR
The reported results underline how an accurate reproduction of the experimental spectrum can only be obtained by going beyond oversimplified methods and illustrates the potential of the computational investigation, which can shed light on the information hidden in experimental spectra.Abstract:
A detailed computational characterization of the one-photon absorption spectrum of a 2-((E)-2-[2,2′]-bithiophenyl-5-yl-vinyl)-1-methyl-quinolinium cation in acetonitrile solution is presented. The main physico-chemical effects (solvation, vibronic progression) affecting the band position and shape are progressively introduced in the computational model, highlighting their relative role in the spectral profile. The reported results underline how an accurate reproduction of the experimental spectrum can only be obtained by going beyond oversimplified methods. Moreover, the deep interplay between the solvent effects and nuclear rearrangements permits the negative solvatochromism exhibited by hypsochromic molecules to be explained. This illustrates the potential of the computational investigation, which can shed light on the information hidden in experimental spectra.read more
Citations
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Journal ArticleDOI
Interplay between conformational and solvent effects in UV-visible absorption spectra: curcumin tautomers as a case study
TL;DR: The obtained results highlight that for both tautomers specific solute-solvent hydrogen-bond interactions play a minor role with respect to conformational and electrostatic effects.
Journal ArticleDOI
Electronic transitions for a fully polarizable QM/MM approach based on fluctuating charges and fluctuating dipoles: Linear and corrected linear response regimes
Tommaso Giovannini,Rosario Roberto Riso,Matteo Ambrosetti,Alessandra Puglisi,Chiara Cappelli +4 more
TL;DR: Giovannini et al. as discussed by the authors extended the fully polarizable Quantum Mechanics/Molecular Mechanics (QM/MM) approach based on fluctuating charges and fluctuating dipoles to the calculation of vertical excitation energies of solvated molecular systems.
Journal ArticleDOI
Simulating vertical excitation energies of solvated dyes: From continuum to polarizable discrete modeling
Tommaso Giovannini,Marina Macchiagodena,Matteo Ambrosetti,Alessandra Puglisi,Piero Lafiosca,Giulia Lo Gerfo,Franco Egidi,Chiara Cappelli +7 more
Journal ArticleDOI
Electronic Transitions for a Fully Polarizable QM/MM Approach Based on Fluctuating Charges and Fluctuating Dipoles: Linear and Corrected Linear Response Regimes
Tommaso Giovannini,Rosario Roberto Riso,Matteo Ambrosetti,Alessandra Puglisi,Chiara Cappelli +4 more
TL;DR: In this article, a fully polarizable QM/MM approach based on fluctuating charges and fluctuating dipoles is extended to the calculation of vertical excitation energies of solvated molecular systems.
Journal ArticleDOI
Absorption spectra of xanthines in aqueous solution: a computational study.
TL;DR: A detailed computational analysis of the UV/Vis spectra of caffeine, paraxanthine and theophylline in aqueous solution highlights the role of electrostatic, polarization and hydrogen boding solute-solvent interactions.
References
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TL;DR: In this article, a semi-empirical exchange correlation functional with local spin density, gradient, and exact exchange terms was proposed. But this functional performed significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.
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The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
Yan Zhao,Donald G. Truhlar +1 more
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A New Mixing of Hartree-Fock and Local Density-Functional Theories
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Quantum mechanical continuum solvation models.
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Journal ArticleDOI
Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions.
TL;DR: The SMD model may be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space, including, for example, the conductor-like screening algorithm.