Geometries and properties of excited states in the gas phase and in solution: Theory and application of a time-dependent density functional theory polarizable continuum model

Scalmani, Giovanni; Frisch, Michael J.; Mennucci, Benedetta; Tomasi, Jacopo; Cammi, Roberto; Barone, Vincenzo

doi:doi:10.1063/1.2173258

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Simulation of x-ray absorption near-edge spectra and x-ray fluorescence spectra of optically excited molecules

The x-ray absorption near-edge spectra (XANES) and fluorescence spectra of molecules in the ground state and optically excited states are computed using time-dependent density functional theory and time-dependent Hartree-Fock theory. The calculated XANES spectra of optically excited methanol, benzonitrile, hydrogen sulphide, and titanium tetrachloride and the fluorescence spectra of optically excited methanol can be used to simulate ultrafast optical pump/x-ray probe experiments.

Scaling down the Perdew-Zunger self-interaction correction in many-electron regions

Semilocal density functional approximations (DFAs) for the exchange-correlation energy suffer from self-interaction error, which is believed to be the cause of many of the failures of common DFAs, such as poor description of charge transfer and transition states of chemical reactions. The standard self-interaction correction (SIC) of Perdew and Zunger mends some of these failures but spoils such essential properties as thermochemistry and equilibrium bond lengths. The Perdew-Zunger SIC seems to...

In this paper we present the theory and implementation of analytic derivatives of time-dependent density functional theory (TDDFT) excited states energies, both in vacuo and including solvent effects by means of the polarizable continuum model. The method is applied to two case studies: p-nitroaniline and 4-(dimethyl)aminobenzonitrile. For both molecules PCM-TDDFT is shown to be successful in supporting the analysis of experimental data with useful insights for a better understanding of photophysical and photochemical pathways in solution.

Article Outline

INTRODUCTION
THEORY
1. The basic PCM theory
2. Excitation energies within the PCM-TDDFT framework
3. Analytical gradient of the excited state energy in the gas phase and in solution
4. The relaxed density and the first order properties
ENERGIES, STRUCTURES, AND PROPERTIES OF PNA AND DMABN EXCITED STATES
1. PNA
2. DMABN
CONCLUSIONS

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KEYWORDS and PACS

Keywords

organic compounds, molecular configurations, excited states, density functional theory, solvent effects

PACS

31.15.E-

Density-functional theory
31.70.Dk

Environmental and solvent effects
33.15.Bh

General molecular conformation and symmetry; stereochemistry

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http://link.aip.org/link/doi/10.1063/1.2173258

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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