Efficient methods to calculate dynamic hyperpolarizability tensors by time-dependent density-functional theory

Heinze, H.; Sala, Fabio Della; Görling, Andreas

doi:10.1063/1.1476014

Cited by 26 publications

(10 citation statements)

References 46 publications

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“…Although this does not mean a complete failure as in the case of so-called longrange charge-transfer excitations, [65][66][67][68][69][70][71] it is well-known that such excitation energies in nitrobenzenes are underestimated by TDDFT. 72,73 In order to identify problems related to the CT character of certain transitions, we also calculated excitation energies using the B3LYP hybrid functional for a structure optimized with B3LYP and a triple-z valence plus polarization (TZVP) basis set as implemented in TURBOMOLE. 45 The resulting excitations were mapped to the SAOP results on the basis of the orbital transitions involved (see Table 2).…”

Section: Tddft Calculationsmentioning

confidence: 99%

The ketene intermediate in the photochemistry of ortho-nitrobenzaldehyde

Laimgruber

Schmierer

Gilch

et al. 2008

Phys. Chem. Chem. Phys.

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The first intermediate of the photochemical transformation of ortho-nitrobenzaldehyde to ortho-nitrosobenzoic acid in acetonitrile solvent has been characterized by femtosecond spectroscopy and time-dependent density functional theory (TDDFT) calculations. Femtosecond stimulated Raman spectroscopy (FSRS) indicates that this intermediate adopts a ketene structure. This assignment is supported by the TDDFT results. A kinetic analysis of FSRS and transient absorption data points to two channels for the formation of the ketene. For the predominating first channel the formation takes 0.4 ps. For the second channel it is much slower and takes 220 ps. We assign the first channel to a reaction via an excited singlet state. The second one might involve a triplet state.

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Section: Tddft Calculationsmentioning

confidence: 99%

The ketene intermediate in the photochemistry of ortho-nitrobenzaldehyde

Laimgruber

Schmierer

Gilch

et al. 2008

Phys. Chem. Chem. Phys.

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show abstract

“…The use of TD-DFT for calculating molecular response properties in the gas-phase has been shown to be accurate for small and medium size molecules, especially if one uses recently developed density functionals. [9][10][11][12][13][14][15][16][17][18] Therefore, the extension of TD-DFT to treat also molecules in solution is of great interest.…”

Section: Introductionmentioning

confidence: 99%

A discrete solvent reaction field model for calculating frequency-dependent hyperpolarizabilities of molecules in solution

Jensen

Duijnen

Snijders

2003

The Journal of Chemical Physics

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Articles you may be interested inDensity functional theory calculations of dynamic first hyperpolarizabilities for organic molecules in organic solvent: Comparison to experiment A discrete solvent reaction field model for calculating molecular linear response properties in solution Calculation of frequency-dependent second hyperpolarizabilities for electric field induced second harmonic generation in the second-order Mo/ller-Plesset perturbation theory Calculation of frequency-dependent first hyperpolarizabilities using the second-order Møller-Plesset perturbation theoryWe present a discrete solvent reaction field ͑DRF͒ model for the calculation of frequency-dependent hyperpolarizabilities of molecules in solution. In this model the solute is described using density functional theory ͑DFT͒ and the discrete solvent molecules are described with a classical polarizable model. The first hyperpolarizability is obtained in an efficient way using time-dependent DFT and the (2nϩ1) rule. The method was tested for liquid water using a model in which a water molecule is embedded in a cluster of 127 classical water molecules. The frequency-dependent first and second hyperpolarizabilities related to the electric field induced second harmonic generation ͑EFISH͒ experiment, were calculated both in the gas phase and in the liquid phase. For water in the gas phase, results are obtained in good agreement with correlated wave function methods and experiments by using the so-called shape-corrected exchange correlation ͑xc͒-potentials. In the liquid phase the effect of using asymptotically correct functionals is discussed. The model reproduced the experimentally observed sign change in the first hyperpolarizaibility when going from the gas phase to the liquid phase. Furthermore, it is shown that the first hyperpolarizability is more sensitive to damping of the solvent-solute interactions at short range than the second hyperpolarizability.

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“…The use of TD-DFT for calculating molecular response properties in the gas phase has been shown to be accurate for small and medium size molecules, especially if one uses recently developed density functionals. [8][9][10][11][12][13][14][15][16][17] In recent years applications of TD-DFT to calculate properties of molecules in solution has also been presented. 18 -27 Among the methods for treating solvent effect on molecules are the combined quantum mechanical and molecular mechanics ͑QM/MM͒ models.…”

Section: Introductionmentioning

confidence: 99%

Microscopic and macroscopic polarization within a combined quantum mechanics and molecular mechanics model

Jensen

Swart

Duijnen

2004

The Journal of Chemical Physics

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A polarizable quantum mechanics and molecular mechanics model has been extended to account for the difference between the macroscopic electric field and the actual electric field felt by the solute molecule. This enables the calculation of effective microscopic properties which can be related to macroscopic susceptibilities directly comparable with experimental results. By seperating the discrete local field into two distinct contribution we define two different microscopic properties, the so-called solute and effective properties. The solute properties account for the pure solvent effects, i.e., effects even when the macroscopic electric field is zero, and the effective properties account for both the pure solvent effects and the effect from the induced dipoles in the solvent due to the macroscopic electric field. We present results for the linear and nonlinear polarizabilities of water and acetonitrile both in the gas phase and in the liquid phase. For all the properties we find that the pure solvent effect increases the properties whereas the induced electric field decreases the properties. Furthermore, we present results for the refractive index, third-harmonic generation ͑THG͒, and electric field induced second-harmonic generation ͑EFISH͒ for liquid water and acetonitrile. We find in general good agreement between the calculated and experimental results for the refractive index and the THG susceptibility. For the EFISH susceptibility, however, the difference between experiment and theory is larger since the orientational effect arising from the static electric field is not accurately described.

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Efficient methods to calculate dynamic hyperpolarizability tensors by time-dependent density-functional theory

Cited by 26 publications

References 46 publications

The ketene intermediate in the photochemistry of ortho-nitrobenzaldehyde

The ketene intermediate in the photochemistry of ortho-nitrobenzaldehyde

A discrete solvent reaction field model for calculating frequency-dependent hyperpolarizabilities of molecules in solution

Microscopic and macroscopic polarization within a combined quantum mechanics and molecular mechanics model

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