Toward effective and reliable fluorescence energies in solution by a new state specific polarizable continuum model time dependent density functional theory approach

Improta, Roberto; Scalmani, Giovanni; Frisch, Michael J.; Barone, Vincenzo

doi:doi:10.1063/1.2757168

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Hydration properties of magnesium and calcium ions from constrained first principles molecular dynamics

We studied the solvation structures of the divalent metal cations Mg2+ and Ca2+ in ambient water by applying a Car-Parrinello-based constrained molecular dynamics method. By employing the metal-water oxygen coordination number as a reaction coordinate, we could identify distinct aqua complexes characterized by structural variations of the first coordination shell. In particular, our estimated free-energy profile clearly shows that the global minimum for Mg2+ is represented by a rather stable si...

Continuum limit semiclassical initial value representation for dissipative systems

In this paper, we consider a dissipative system in which the system is coupled linearly to a harmonic bath. In the continuum limit, the bath is defined via a spectral density and the classical system dynamics is given in terms of a generalized Langevin equation. Using the path integral formulation and factorized initial conditions, it is well known that one can integrate out the harmonic bath, leaving only a path integral over the system degrees of freedom. However, the semiclassical initial va...

A state specific (SS) model for the inclusion of solvent effects in time dependent density functional theory (TD-DFT) computations of emission energies has been developed and coded in the framework of the so called polarizable continuum model (PCM). The new model allows for a rigorous and effective treatment of dynamical solvent effects in the computation of fluorescence and phosphorescence spectra in solution, and it can be used for studying different relaxation time regimes. SS and conventional linear response (LR) models have been compared by computing the emission energies for different benchmark systems (formaldehyde in water and three coumarin derivatives in ethanol). Special attention is given to the influence of dynamical solvation effects on LR geometry optimizations in solution. The results on formaldehyde point out the complementarity of LR and SS approaches and the advantages of the latter model especially for polar solvents and/or weak transitions. The computed emission energies for coumarin derivatives are very close to their experimental counterparts, pointing out the importance of a proper treatment of nonequilibrium solvent effects on both the excited and the ground state energies. The availability of SS-PCM/TD-DFT models for the study of absorption and emission processes allows for a consistent treatment of a number of different spectroscopic properties in solution.

Article Outline

INTRODUCTION
THEORETICAL BACKGROUND
COMPUTATIONAL DETAILS
RESULTS
1. Formaldehyde
2. Geometry optimizations
3. Coumarin
DISCUSSION AND CONCLUDING REMARKS

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KEYWORDS and PACS

Keywords

density functional theory, fluorescence, organic compounds, phosphorescence, solvent effects

PACS

78.55.Bq

Liquids

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http://link.aip.org/link/doi/10.1063/1.2757168

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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