Solvent Dependence of the First Molecular Hyperpolarizability of <i>p</i>-Nitroaniline Revisited

Woodford, Jeffrey N.; Pauley, Mark A.; Wang, C. H.

doi:10.1021/jp9639861

Cited by 98 publications

(46 citation statements)

References 9 publications

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“…We measured the dynamic first hyperpolarizability of pNA dissolved in toluene by using pNA dissolved in DMSO as reference. 66 The value obtained is around (18 ± 3) × 10 −30 cm 5 /esu which is close to the ones reported by Marks et al at 900 nm. 67 The angular coefficient is obtained from the empirical relation between I(2ω)/I 2 (ω) (where I(2ω) is the intensity from the scattered beam at 2ω and I (ω) corresponds to the intensity of excitation beam) and sample concentration.…”

Section: B First-order Hyperpolarizability-experimental Resultssupporting

confidence: 90%

Experimental and theoretical investigation of the first-order hyperpolarizability of a class of triarylamine derivatives

Silva

Fonseca

Vivas

et al. 2015

The Journal of Chemical Physics

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This paper reports on the static and dynamic first-order hyperpolarizabilities of a class of push-pull octupolar triarylamine derivatives dissolved in toluene. We have combined hyper-Rayleigh scattering experiment and the coupled perturbed Hartree-Fock method implemented at the Density Functional Theory (DFT) level of theory to determine the static and dynamic (at 1064 nm) first-order hyperpolarizability (βHRS) of nine triarylamine derivatives with distinct electron-withdrawing groups. In four of these derivatives, an azoaromatic unit is inserted and a pronounceable increase of the first-order hyperpolarizability is reported. Based on the theoretical results, the dipolar/octupolar character of the derivatives is determined. By using a polarizable continuum model in combination with the DFT calculations, it was found that although solvated in an aprotic and low dielectric constant solvent, due to solvent-induced polarization and the frequency dispersion effect, the environment substantially affects the first-order hyperpolarizability of all derivatives investigated. This statement is supported due to the solvent effects to be essential for the better agreement between theoretical results and experimental data concerning the dynamic first-order hyperpolarizability of the derivatives. The first-order hyperpolarizability of the derivatives was also modeled using the two- and three-level models, where the relationship between static and dynamic first hyperpolarizabilities is given by a frequency dispersion model. Using this approach, it was verified that the dynamic first hyperpolarizability of the derivatives is satisfactorily reproduced by the two-level model and that, in the case of the derivatives with an azoaromatic unit, the use of a damped few-level model is essential for, considering also the molecular size of such derivatives, a good quantitative agreement between theoretical results and experimental data to be observed.

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Section: B First-order Hyperpolarizability-experimental Resultssupporting

confidence: 90%

Experimental and theoretical investigation of the first-order hyperpolarizability of a class of triarylamine derivatives

Silva

Fonseca

Vivas

et al. 2015

The Journal of Chemical Physics

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“…This finding shows that our usual way of thinking about excited states of push-pull molecules can be erroneous, and lead to dubious predictions and intuitions. p-Nitroaniline is a prototypical push-pull molecule exhibiting a large first hyperpolarizability [5][6][7][8][9][10][11] and nonlinear optical properties with possible applications for electrooptic and second-harmonic generation materials. As a model system, PNA has long been studied both experimentally [4,[12][13][14][15][16][17][18][19][20][21][22] and theoretically.…”

Section: Introductionmentioning

confidence: 99%

Is Our Way of Thinking about Excited States Correct? Time‐Resolved Dispersive IR Study on p‐Nitroaniline

Narra¹,

Chang²,

Witek³

et al. 2012

Chemistry A European J

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Low-lying excited electronic states of an important class of molecules known as push-pull chromophores are central to understanding their potential nonlinear optical properties. Here we report that a combination of high-sensitivity nanosecond time-resolved dispersive IR spectroscopy and DFT calculations on p-nitroaniline (PNA), a prototypical push-pull molecule, reveals that PNA in the lowest excited triplet state has a partial quinoid structure. In this structure, the quinoid configuration is restricted to a part of the phenyl ring adjacent to the NO(2) group. The partial quinoid structure of PNA cannot be explained by a commonly used hybrid of a neutral form and a zwitterionic charge-transfer form. Our findings not only cast doubt on the general applicability of the classical way of looking at excited states, based exclusively on characteristic resonance structures, but also provide deeper insights into excited-state structure of highly polarizable molecular systems.

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“…18 The strong solvent dependence is usually described in terms of a two-state model. 14,[17][18][19][20] Recently, an experimental study found for solvents not forming H bonds a a͒ good linear correlation of the form ␤ = ␤ gas + a ͱ s / V s where, s is the dipole moment of the solvent in the gas phase, V s the molar volume in the liquid state, and ␤ gas is considered to be the first hyperpolarizability in the gas phase. 17 The references used in the measurements were the first hyperpolarizability of p-NA in 1,4-dioxane at 1064 nm adopted from Ref.…”

Section: Introductionmentioning

confidence: 99%

The first hyperpolarizability of p-nitroaniline in 1,4-dioxane: A quantum mechanical/molecular mechanics study

Jensen

Duijnen

2005

The Journal of Chemical Physics

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In this work we have investigated the first hyperpolarizability of pNA in 1,4-dioxane solution using a quantum mechanics/molecular mechanics (QM/MM) model. The particular model adopted is the recently developed discrete solvent reaction field (DRF) model. The DRF model is a polarizable QM/MM model in which the QM part is treated using time-dependent density-functional theory and local-field effects are incorporated. This allows for direct computation of molecular effective properties which can be compared with experimental results. The solvation shift for the first hyperpolarizability is calculated to be 30% which is in good agreement with the experimental results. However, the calculated values, both in the gas phase and in solution, are by a factor of 2 larger than the experimental ones. This is in contrast to the calculation of the first hyperpolarizability for several small molecules in the gas phase where fair agreement is found with experimental. The inclusion of local-field effects in the calculations was found to be crucial and neglecting them led to results which are significantly larger. To test the DRF model the refractive index of liquid 1,4-dioxane was also calculated and found to be in good agreement with experiment.

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Solvent Dependence of the First Molecular Hyperpolarizability of p-Nitroaniline Revisited

Cited by 98 publications

References 9 publications

Experimental and theoretical investigation of the first-order hyperpolarizability of a class of triarylamine derivatives

Experimental and theoretical investigation of the first-order hyperpolarizability of a class of triarylamine derivatives

Is Our Way of Thinking about Excited States Correct? Time‐Resolved Dispersive IR Study on p‐Nitroaniline

The first hyperpolarizability of p-nitroaniline in 1,4-dioxane: A quantum mechanical/molecular mechanics study

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