Simple Scheme To Evaluate Crystal Nonlinear Susceptibilities: Semiempirical AM1 Model Investigation of 3-Methyl-4-nitroaniline Crystal

Castet, Frédéric; Champagne, Benoı̂t

doi:10.1021/jp003746s

Cited by 63 publications

(51 citation statements)

References 39 publications

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“…This approximation was demonstrated in a series of works [40][41][42] to be a good choice combining both the quality of the results and the sparing of computational resources for the investigation of NLO responses in medium-and large-size systems. Two second-order NLO responses, derived from specific sums of the first hyperpolarizability tensor components, were investigated in the present work.…”

Section: Methodsmentioning

confidence: 99%

“…Indeed, when packing D/A compounds laterally, both dressing and local field effects are detrimental to the first hyperpolarizability. [41] As a consequence of these packing effects, the ordering of the b HRS magnitude is modified when going from the molecular units to the oligomers containing ten units. However, the largest hyper-Rayleigh response is still associated with substitutions by amino groups.…”

mentioning

confidence: 99%

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Theoretical Investigation of the Second‐Order Nonlinear Optical Properties of Helical Pyridine–Pyrimidine Oligomers

Botek

Castet

Champagne

2006

Chemistry A European J

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The structure and second-order nonlinear optical properties of a series of helical pyridine-pyrimidine oligomers recently synthesized by Barboiu and Lehn have been investigated theoretically by combining molecular mechanics and quantum chemistry approaches. In the absence of substituents, the hyper-Rayleigh scattering response (betaHRS) and the projection of the first hyperpolarizability on the dipole moment (beta||) exhibit periodic variations with chain length, but these nonlinear optical responses remain small. The first hyperpolarizabilities can, however, be enhanced by adding substituents. The greatest enhancement is obtained by substituting the pyrimidine groups by donor groups. Moreover, regular distributions of the donor groups around the helices enable the design of supramolecular structures exhibiting dipolar, octupolar or Lambda-shaped nonlinear optical characters, evident from the values of the depolarization ratios in hyper-Rayleigh scattering. Therefore this theoretical investigation demonstrates the potential of helical structures for the organization of chromophores in such a way that they exhibit large and specific second-order nonlinear optical responses.

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

Theoretical Investigation of the Second‐Order Nonlinear Optical Properties of Helical Pyridine–Pyrimidine Oligomers

Botek

Castet

Champagne

2006

Chemistry A European J

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“…The linear and nonlinear optical properties of MNA have already been the topic of several experimental 30-34 and theoretical [11][12][13][14] studies. MNA crystallizes in a monoclinic system and has been described in equivalent space groups Cc, An, and Ia with 4 molecules per unit cell ( Figure 1).…”

Section: A 2-methyl-4-nitroanilinementioning

confidence: 99%

“…Note that MNA, owing to its small size, is often considered as a prototype NLO molecular crystal and has been the subject of several theoretical investigations, using different types of approaches. [11][12][13][14] In addition, owing to their relationships with χ (2) , the linear susceptibility χ (1) and the refractive indices are also calculated and analyzed. The unit cells of the crystals are presented in Figure 1 while the single molecules are sketched in Figure 2.…”

Section: Introductionmentioning

confidence: 99%

Investigation of the linear and second-order nonlinear optical properties of molecular crystals within the local field theory

Seidler

Stadnicka

Champagne

2013

The Journal of Chemical Physics

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In this paper it is shown that modest calculations combining first principles evaluations of the molecular properties with electrostatic interaction schemes to account for the crystal environment effects are reliable for predicting and interpreting the experimentally measured electric linear and second-order nonlinear optical susceptibilities of molecular crystals within the experimental error bars. This is illustrated by considering two molecular crystals, namely: 2-methyl-4-nitroaniline and 4-(N,N-dimethylamino)-3-acetamidonitrobenzene. Three types of surrounding effects should be accounted for (i) the polarization due to the surrounding molecules, described here by static electric fields originating from their electric dipoles or charge distributions, (ii) the intermolecular interactions, which affect the geometry and particularly the molecular conformation, and (iii) the screening of the external electric field by the constitutive molecules. This study further highlights the role of electron correlation on the linear and nonlinear responses of molecular crystals and the challenge of describing frequency dispersion.

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“…Indeed, at several instances, the TDHF and coupled-perturbed Hartree-Fock (CPHF) schemes employing the AM1 Hamiltonian have been found to reproduce efficiently (hyper)polarizabilities evaluated at ab initio correlated levels. [31] The second-order NLO responses under investigation are: Figure 1. Structure of tetrathia- [7]-helicene, numbering of the substituent positions, and definition of the radial and axial components.…”

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Theoretical Design of Substituted Tetrathia‐[7]‐Helicenes with Large Second‐Order Nonlinear Optical Responses

et al. 2004

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Second-order nonlinear optical (NLO) materials have attracted a lot of interest because of foreseeable applications in optoelectronic technology.[1] In particular, organic compounds are attractive for this purpose because of their large and fast responses combined with the flexibility of organic synthesis which hastens the design of new chromophores. The first generation of NLO organic chromophores consists of one-dimensional (1D) p-conjugated systems end-capped with donor (D) and acceptor (A) moieties. Experimental and theoretical work has shown during the last decades how to choose the D/A strengths and p segments for optimizing the second-order NLO responses.[2-4] Later, two-dimensional (2D) octupolar molecules such as 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) were shown to exhibit second-order NLO responses that can be as large as those of their dipolar analogues. [5][6][7] In addition, with these 2D structures, some of the limitations of the 1D dipolar structures were displaced, if not overcome. Indeed, 1D compounds suffer from the transparency-efficiency tradeoff, which is difficult to achieve because the desirable increase in b(the first hyperpolarizability) is accompanied by a bathochromatic shift of the electronic transitions. Moreover, their dipolar nature and the predominance of dipole-dipole intermolecular interactions favor the formation of centrosymmetric crystal arrangements which exhibit no second harmonic generation (SHG) responses. In addition, phase-matching conditions cause only a fraction of the microscopic response to be preserved at the macroscopic scale.[8] On the other hand, octupolar compounds present an improved nonlinearity/transparency tradeoff, enable non-centrosymmetric crystal structures owing to their lack of permanent dipole moment, and present large offdiagonal b tensor components that can give rise to large macroscopic SHG responses. [6] [a] Dr.

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Simple Scheme To Evaluate Crystal Nonlinear Susceptibilities: Semiempirical AM1 Model Investigation of 3-Methyl-4-nitroaniline Crystal

Cited by 63 publications

References 39 publications

Theoretical Investigation of the Second‐Order Nonlinear Optical Properties of Helical Pyridine–Pyrimidine Oligomers

Theoretical Investigation of the Second‐Order Nonlinear Optical Properties of Helical Pyridine–Pyrimidine Oligomers

Investigation of the linear and second-order nonlinear optical properties of molecular crystals within the local field theory

Theoretical Design of Substituted Tetrathia‐[7]‐Helicenes with Large Second‐Order Nonlinear Optical Responses

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