Hyperpolarizability density analysis of the enhancement of second hyperpolarizability of π‐conjugated oligomers by intermolecular interaction

Nakano, Masayoshi; Kishi, Ryohei; Nitta, Tomoshige; Champagne, Benoı̂t; Botek, Edith; Yamaguchi, Kizashi

doi:10.1002/qua.20378

Cited by 19 publications

(17 citation statements)

References 39 publications

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“…We further analyzed the spatial electronic contribution of the hyperpolarizability density , for macrocyclic [32]octaphyrins(1.0.1.0.1.0.1.0) to clarify the characteristic of their nonlinearity. The schematic diagrams of the integrand of β zzz (∞), namely, local contribution function of the first hyperpolarizability [− z ρ zz (2) ( r ⃗)], for the studied octaphyrins are rendered in Figure .…”

Section: Resultsmentioning

confidence: 99%

Controllable Photophysical and Nonlinear Properties in Conformation Isomerization of Macrocyclic [32]Octaphyrin(1.0.1.0.1.0.1.0) Involving Hückel and Möbius Topologies

Liu

Tian²

2019

J. Phys. Chem. C

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The conversions of photophysical and nonlinear optical (NLO) properties in [32]octaphyrins(1.0.1.0.1.0.1.0) following macrocyclic isomerization between Huckel and Mobius topologies have been studied in detail by means of quantum chemistry calculations. Compared to their quasi-planar analogues, the twisted Mobius and the figure-eight Huckel conformers exhibit red-and blue-shifted absorptions, respectively. The fluorescence emissions of Huckel topological molecules are likely to be from the second excited state, while the Mobius ones should emit photons from the first excited state by following Kasha's rule. The average polarizabilities of octaphyrins reveal certain regularity with regard to their topologies, but is not particularly large; with the π-conjugation enhanced, the polarizability value increased moderately. The static firstand second-order hyperpolarizabilities of Mobius conformations are almost all much higher than those of Huckel conformers, and the figureeight Huckel structures exhibit relatively high values than the quasi-planar Huckel ones. Regarding the frequency dispersions under the incident light, the strong optical resonance effects were found on the firstand second-order hyperpolarizability of molecules, which contrast with the fact that it has modest influences on the average polarizability. The primary cause of the performance differences in optical properties of the octaphyrins has also been probed from different perspectives by various methods of electronic wavefunction analysis. Generally, we confirm that the topological transformation of expanded porphyrins can be used as a special switch to trigger various optical properties.

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Section: Resultsmentioning

confidence: 99%

Controllable Photophysical and Nonlinear Properties in Conformation Isomerization of Macrocyclic [32]Octaphyrin(1.0.1.0.1.0.1.0) Involving Hückel and Möbius Topologies

Liu

Tian²

2019

J. Phys. Chem. C

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“…In order to interpret these results, we also studied the spatial distribution of the dielectric properties using the concepts of polarizability-and hyperpolarizability-densities, as well as first-and second-order electricfield-perturbed densities. 8,9 In addition, we also investigated the dependence of polarization properties on the choice of exchange-correlation (XC) functionals and the correlation level by means of DFT, HF, MP2 and CCSD methods. We also briefly discuss the dependence of the results on the molecular geometry, which was found to have a significant influence on the calculated hyperpolarizability.…”

Section: Introductionmentioning

confidence: 99%

Basis set effects on the hyperpolarizability of CHCl3: Gaussian-type orbitals, numerical basis sets and real-space grids

Vila

Strubbe

Takimoto

et al. 2010

The Journal of Chemical Physics

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Calculations of the hyperpolarizability are typically much more difficult to converge with basis set size than the linear polarizability. In order to understand these convergence issues and hence obtain accurate ab initio values, we compare calculations of the static hyperpolarizability of the gas-phase chloroform molecule (CHCl 3 ) using three different kinds of basis sets: Gaussian-type orbitals, numerical basis sets, and real-space grids. Although all of these methods can yield similar results, surprisingly large, diffuse basis sets are needed to achieve convergence to comparable values.These results are interpreted in terms of local polarizability and hyperpolarizability densities. We find that the hyperpolarizability is very sensitive to the molecular structure, and we also assess the significance of vibrational contributions and frequency dispersion.

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“…Since the Hückel investigation of a neutral soliton defect in polyacetylene by Pople and Walmsley 4, during the past decades, quantum chemistry has addressed many questions concerning defects in conducting polymers and, in particular, in polyacetylene 5–9. Among these, recent contributions have dealt with the dynamics of the positively charged solitonic defect, the linear and nonlinear optical properties, as well as the effects of chain length, counterion, and crystal packing on the latter 10–17. These studies have discussed the relationship between the electronic charge added to or removed from the conjugated chain and the variation of the second hyperpolarizability.…”

Section: Introductionmentioning

confidence: 99%

Charge distributions in polyacetylene chains containing a positively charged defect

Monev

Spassova

Champagne

2005

Int J of Quantum Chemistry

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ABSTRACT:We present a comparative study of the AIM, CHELPG, GAPT, MK, Mulliken, NPA, and RESP charge distributions associated with a positively charged soliton on increasingly large trans-polyacetylene chains, at HF, MP2, and DFT levels of theory. The charge storage in the soliton-bearing systems is explored in detail, including charge magnitude, charge separation, charge alternation, and chain length effects. The grouping of the charge distributions at a given level of theory, as well as the sensitivity of a given charge distribution to the inclusion of electron correlation in its computation, are investigated using similarity analysis. Several of the charge definitions have been applied for the first time for charged soliton-bearing systems, and there are substantial differences between the charge distributions for the charged and neutral systems. Thus, AIM charges are no longer one of the largest charge values, the AIM charges can be in counterphase with other definitions, and the GAPT charges for neutral systems are quite different from the GAPT charges for charged systems, e.g., the magnitudes of the GAPT charges are anomalously large and increase with the size of the charged system.

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Hyperpolarizability density analysis of the enhancement of second hyperpolarizability of π‐conjugated oligomers by intermolecular interaction

Cited by 19 publications

References 39 publications

Controllable Photophysical and Nonlinear Properties in Conformation Isomerization of Macrocyclic [32]Octaphyrin(1.0.1.0.1.0.1.0) Involving Hückel and Möbius Topologies

Controllable Photophysical and Nonlinear Properties in Conformation Isomerization of Macrocyclic [32]Octaphyrin(1.0.1.0.1.0.1.0) Involving Hückel and Möbius Topologies

Basis set effects on the hyperpolarizability of CHCl3: Gaussian-type orbitals, numerical basis sets and real-space grids

Charge distributions in polyacetylene chains containing a positively charged defect

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