Quantum Chemical Calculations of the First- and Second-Order Hyperpolarizabilities of Molecules in Solutions

Bartkowiak, Wojciech; Zaleśny, Robert; Niewodniczański, and W.; Leszczyński, Jerzy

doi:10.1021/jp010682s

Cited by 45 publications

(25 citation statements)

References 88 publications

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“…In particular, numerous aspects affecting the nonlinear absorption, such as molecular symmetry, molecular planarity and extension of the conjugation length of the compounds have been considered. [7][8][9] More recently, theoretical methods have been employed to support the understanding of experimental 2PA spectrum of several compounds, 8,[10][11][12] including azoaromatic compounds, which have also been the target of theoretical studies. [11][12][13] Among several theoretical methods used to study electronic transitions of compounds, the density functional theory ͑DFT͒ combined with linear response function formalism 14 has been shown to provide accurate excitation energies particularly when employing hybrid exchange-correlation functionals.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical study of one- and two-photon absorption spectra of azoaromatic compounds

Silva

Krawczyk

Bartkowiak

et al. 2009

The Journal of Chemical Physics

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Following the excited state relaxation dynamics of indole and 5-hydroxyindole using time-resolved photoelectron spectroscopy J. Chem. Phys. 135, 194307 (2011) Population inversion of molecular nitrogen in an Ar: N2 mixture by selective resonance-enhanced multiphoton ionization J. Appl. Phys. 110, 083112 (2011) Control of vibronic excitation using quantum-correlated photons J. Chem. Phys. 135, 164304 (2011) Resonant two-photon ionization spectroscopy of jet-cooled PdSi J. Chem. Phys. 135, 134308 (2011) Optical purification of a mixture of chiral forms by dimer formation J. Chem. Phys. 135, 124304 (2011) Additional information on J. Chem. Phys. In this study, the one-and two-photon absorption spectra of seven azoaromatic compounds ͑five pseudostilbenes-type and two aminoazobenzenes͒ were theoretically investigated using the density functional theory combined with the response functions formalism. The equilibrium molecular structure of each compound was obtained at three different levels of theory: Hartree-Fock, density functional theory ͑DFT͒, and Møller-Plesset 2. The effect of solvent on the equilibrium structure and the electronic transitions of the compounds were investigated using the polarizable continuum model. For the one-photon absorption, the allowed → ‫ء‬ transition energy showed to be dependent on the molecular structures and the effect of solvent, while the n → ‫ء‬ and → ‫ء‬ ͑n͒ transition energies exhibited only a slight dependence. An inversion between the bands corresponding to the → ‫ء‬ and n → ‫ء‬ states due to the effect of solvent was observed for the pseudostilbene-type compounds. To characterize the allowed two-photon absorption transitions for azoaromatic compounds, the response functions formalism combined with DFT using the hybrid B3LYP and PBE0 functionals and the long-range corrected CAM-B3LYP functional was employed. The theoretical results support the previous findings based on the three-state model. The model takes into account the ground and two electronic excited states and has already been used to describe and interpret the two-photon absorption spectrum of azoaromatic compounds. The highest energy two-photon allowed transition for the pseudostilbene-type compounds shows to be more effectively affected ͑ϳ20%͒ by the torsion of the molecular structure than the lowest allowed transition ͑ϳ10%͒. In order to elucidate the effect of the solvent on the two-photon absorption spectra, the lowest allowed two-photon transition ͑dipolar transition͒ for each compound was analyzed using a two-state approximation and the polarizable continuum model. The results obtained reveal that the effect of solvent increases drastically the two-photon cross-section of the dipolar transition of the pseudostilbene-type compounds. In general, the features of both one-and two-photon absorption spectra of the azoaromatic compounds are well reproduced by the theoretical calculations.

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Section: Introductionmentioning

confidence: 99%

“…20 Moreover, the effect of solvent on the lowest two-photon allowed transition ͑dipolar transition͒ of each compound was analyzed using a two-state approximation. 9,12,21 …”

Section: Introductionmentioning

confidence: 99%

Theoretical study of one- and two-photon absorption spectra of azoaromatic compounds

Silva

Krawczyk

Bartkowiak

et al. 2009

The Journal of Chemical Physics

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“…Most NLO-based applications but also characterizations of the NLO properties are carried out in condensed phase (in solutions, crystals, polymer matrices). The NLO properties of molecules in solutions have been the object of intense investigations [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24], where successive methodological developments have enabled to better understand solvation effects and to more closely account for experimental observations. Many approaches and methodologies have been developed to theoretically study the solvent effects, for example, the models of solvent continuum [4][5][6] and the combined use of quantum mechanics and molecular mechanics (QM/MM) methodologies [7,8].…”

Section: Introductionmentioning

confidence: 99%

The first hyperpolarizability of nitrobenzene in benzene solutions: investigation of the effects of electron correlation within the sequential QM/MM approach

Cardenuto

Champagne

2015

Phys. Chem. Chem. Phys.

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The first hyperpolarizability of nitrobenzene in benzene solutions is evaluated by adopting the sequential-Quantum Mechanics/Molecular Mechanics approach at different correlated wavefunction and density functional theory levels of approximation in order to compare these methods for predicting the solvent effects and in particular the effects of nitrobenzene concentration, which modifies the polarization field due to the surrounding. The liquid configurations are generated using Monte Carlo simulations and the surrounding molecules are represented by point charges, defining an electrostatic embedding. At all levels of approximation, the higher the concentration in nitrobenzene, the larger the first hyperpolarizability of the targeted molecule. At optical frequencies (λ = 1064 nm), for the whole range of concentrations, increasing the amount of Hartree-Fock exchange in the exchange-correlation functional leads to the following observations (i) β∥ and βHRS decrease attaining a minimum at the HF level, (ii) the octupolar component to βHRS increases, (iii) the HRS βsolv/βisol ratio increases, and (iv) the EFISHG βsolv/βisol ratio displays a less systematic behavior. Considering the static properties, for which reference CCSD(T) values have been evaluated, M05-2X, LC-BLYP (μ = 0.33), and M11 are the most reliable exchange-correlation functionals for predicting both βHRS and its evolution as a function of the nitrobenzene concentration whereas in the case of β∥, these are M05-2X, LC-BLYP (μ = 0.28 and 0.33), and CAM-B3LYP.

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“…Moreover, Ray and coworkers [30] studied the first hyperpolarizabilities of a series of benzoic and cinnamic acids in water and found that solvent effects must be considered for accurate calculation of the first hyperpolarizability of these acids. For additional studies on solvent effects refer to [31][32][33].…”

Section: Introductionmentioning

confidence: 99%

Molecular electric properties of nitrogen heterocycles

Safinejad

Asghari-Khiavi

2009

JCM

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Solvent effects on molecular electric properties of several nitrogen heterocycles have been studied using quantum chemical calculations. Two reaction field models including Onsager model and polarizable continuum model have been employed to investigate the reaction field effects. It is observed that dipole moment, polarizability, and total hyperpolarizability of the studied compounds increase with reaction field. Furthermore, ab initio method and perturbation treatment of the Onsager model have been used to evaluate molecular and structural properties of N -bromophthalimide. A very good agreement is observed between the results of the ab initio method and those of the perturbation treatment.

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Quantum Chemical Calculations of the First- and Second-Order Hyperpolarizabilities of Molecules in Solutions

Cited by 45 publications

References 88 publications

Theoretical study of one- and two-photon absorption spectra of azoaromatic compounds

Theoretical study of one- and two-photon absorption spectra of azoaromatic compounds

The first hyperpolarizability of nitrobenzene in benzene solutions: investigation of the effects of electron correlation within the sequential QM/MM approach

Molecular electric properties of nitrogen heterocycles

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