Calculations of second hyperpolarizabilities of some polyenic derivatives

Machado, Ana E. de A.; Gama, A. A. S. da

doi:10.1016/s0166-1280(02)00475-x

Cited by 13 publications

(22 citation statements)

References 29 publications

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“…The overall trend predicted at the PBE1PBE/6‐31G(d)//B3LYP/6‐31G(d) level of calculation is shown in Figure 4(a). β mol decreases with increasing BLA values, as expected for conjugated polymers 87, 88. For molecules I to IV , the NLO response is quite sensitive to the structural changes induced by the substituents, showing a quadratic increase with the respective decrease of the BLA parameter.…”

Section: Resultscontrasting

confidence: 45%

“…Although for π‐conjugated systems it is well known from the literature that the B3LYP functional underestimates the BLA parameter in contrast with the results obtained with other functional, such as M06‐2X and CAM‐B3LYP, and the long‐distance correction DFT scheme,89–92 the results obtained in this work using the B3LYP hybrid functional show that this parameter is strongly correlated with the β mol value, independent on the functional used for the calculation of the hyperpolarizability, predicting the same increasing order of β for the series of substituted oligomers. Early ab initio and semiempirical results for push–pull polyenes showed that the effect is stronger in the region close to the D and A substituents 7, 88. Considering the calculations at the B3LYP/6‐31G(d) level (and also PBE1PBE/6‐31G(d)), we conclude that the conjugated moiety geometry near the acceptor is significantly different from that near the donor group for all disubstituted systems.…”

Section: Resultsmentioning

confidence: 99%

“…Several systems characterized in the literature having the strong acceptor dicyanovinyl display very low energy transitions for the charge transfer processes, which contribute to the increase in the nonlinear coefficients 94, 95. In addition, theoretical studies revealed large nonlinear responses for various polyenic and aniline derivatives with the acceptor dicyanovinyl group 2, 25, 87, 88, 96, 97. Several experimental and theoretical studies have shown that the magnitude of the first hyperpolarizability of organic molecules is associated with lower values of the HOMO–LUMO gap 2, 3, 24, 56, 57, 96–99.…”

Section: Resultsmentioning

confidence: 99%

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Donor–acceptor diethynylsilane oligomers: A second‐order nonlinear optical material

Machado

Souza

Santos

et al. 2011

J Polym Sci B Polym Phys

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The interest in the study of oligomers has been motivated mainly because of their solubility in common solvents and also their capacity to be crystallized, which allowed for chemical processing leading to important applications in the area of material sciences. In this work, we carried out an investigation of polydiethynylsilane (PDES) decamers substituted with electron donor (D) and acceptor (A) groups, which is certainly of relevance, once PDES itself is known to display large third‐order optical susceptibility. Therefore, density functional theory calculations of static first hyperpolarizability (β) were performed using various functionals with the 6‐31G(d) basis set along with correlated MP2 calculation used as reference for comparison. The influence of A and D substituents on the magnitude of β was investigated by matching the acceptor (dicyanovinyl, nitrobenzene) and donor (propyl, propoxy, and phenylamine) groups attached at both ends of the oligomer. The largest β value was predicted for the derivative having the phenylamine and dicyanovinyl groups, which is around 30 times the relative value for the nonsubstituted decamer, what is a very impressive enhancement reported for the first time in the literature, strongly suggesting that disubstituted diethynylsilane decamers are potential building blocks for molecular‐based materials with second‐order nonlinear responses. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1410–1419, 2011

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Section: Resultscontrasting

confidence: 45%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Donor–acceptor diethynylsilane oligomers: A second‐order nonlinear optical material

Machado

Souza

Santos

et al. 2011

J Polym Sci B Polym Phys

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“…This effect has also been reported elsewhere. 68 On the other hand, the NO 2 group does not show this effect, bringing instead a strong intramolecular contribution to the external electric field. For long chains, where the elongation is proportionally less relevant, the slight chain extension effect is no longer sufficient to compete against the strong effect of effective substitution.…”

Section: The Linear Polarizabilitymentioning

confidence: 99%

A systematic analysis of the structure and (hyper)polarizability of donor-acceptor substituted polyacetylenes using a Coulomb-attenuating density functional

Borini

Limacher

Lüthi

2009

The Journal of Chemical Physics

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In this paper we perform a systematic investigation on all-trans polyacetylene chains of different lengths, end-capped with moieties of different donor or acceptor natures and different strengths, to infer useful structure/property relationship rules and behavioral patterns. The values for bond length alternation (BLA), longitudinal polarizability, and first and second hyperpolarizabilities have been computed with the Coulomb-attenuating density function (CAM-B3LYP), using response theory. A comparison of the relative effect that each end-capping combination contributes to BLA, linear, and nonlinear optical coefficients has been performed. This results in useful insights and general rules to ad hoc tailoring the molecular response for a specific characteristic.

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“…35 However, the use of the TDHF within static treatment has produced good results in NLO molecular studies, regarding to the experimental data. [37][38][39][40][41][42][43] The hyperpolarizability tensor β is defined by expanding the dipole moment of a molecule in the presence of an electric field F in a Taylor series (equation 1), where i, j, k, … represent x, y, z, … and p 0 i is the dipole moment in the absence of the field, α is the linear polarizability, β is the first hyperpolarizability and γ is the second hyperpolarizability.…”

Section: Theoretical Detailsmentioning

confidence: 99%

Molecular properties of coordination compounds of the croconate ion with first-row sivalent transition metals: a quantum mechanical study

Ferreira¹,

Santos²,

Almeida³

et al. 2007

J. Braz. Chem. Soc.

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The ground state of all complexes was found to be of high spin, in accordance with the experimental proposal. The calculated structures and vibrational frequencies were also in agreement with experiment, even though comparisons were made with the solid state structure. The calculated nonlinear optical (NLO) properties were for all the compounds analyzed, using the Time Dependent Hartree-Fock (TDHF) method within the static approach, suggesting that these transition metal complexes might be considered as lead molecules to the development of novel based-molecular materials.

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Calculations of second hyperpolarizabilities of some polyenic derivatives

Cited by 13 publications

References 29 publications

Donor–acceptor diethynylsilane oligomers: A second‐order nonlinear optical material

Donor–acceptor diethynylsilane oligomers: A second‐order nonlinear optical material

A systematic analysis of the structure and (hyper)polarizability of donor-acceptor substituted polyacetylenes using a Coulomb-attenuating density functional

Molecular properties of coordination compounds of the croconate ion with first-row sivalent transition metals: a quantum mechanical study

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