Second order optical nonlinearity in octupolar aromatic systems

Joffre, Manuel; Yaron, David; Silbey, R.; Zyss, Joseph

doi:10.1063/1.463768

Cited by 202 publications

(162 citation statements)

References 12 publications

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“…The discovery by Ledoux et al 14 that the symmetrical relative of PNA, 1,3,5-trinitro-2,4,6-triaminobenzene, displays a large SHG efficiency in the solid phase has however led to an upsurge of interest, from both the theoretical and the practical point of view, in the photophysical properties of symmetrical donor-acceptor compounds. [15][16][17][18] In the present work we have investigated the photophysics of PNA and compounds containing symmetrical arrays of N-alkyl substituted PNA moieties, the structures of which are shown in Figure 1. The main method of investigation used was time-resolved microwave conductivity (TRMC) with which short-lived dipolar products of flash photolysis can be monitored.…”

Section: Introductionmentioning

confidence: 99%

Dipolar Triplet States ofp-Nitroaniline andN-Alkyl Derivatives with One-, Two-, and Three-Fold Symmetry

Schuddeboom¹,

Warman²,

Biemans³

et al. 1996

J. Phys. Chem.

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Photoexcitation of p-nitroaniline (PNA) and its N-alkyl derivatives results in the formation of triplet states with dipole moments considerably larger than that of the ground state, as monitored by time-resolved microwave conductivity (TRMC). The triplet state lifetime, τ T , is only 54 ns for PNA in benzene but increases to 1400 ns on N,N-dimethyl substitution and to 275 ns in the more polar solvent p-dioxane. This sensitivity of τ T is attributed to the close proximity of all of the lowest lying singlet and triplet nπ* and ππ* states of PNA, which results in substantial S 1 T T 1 mixing. The dipole moment of the "pure" 3 ππ* state is estimated to be 11 D. Methylene-bridged arrays of PNA moieties with two-and three-fold D n symmetry, 2-PNA and 3-PNA, are also found to have highly dipolar triplet states, indicating that symmetry breaking and exciton localization occur in T 1 . Flip-flop interchange between the resonant dipolar structures is estimated to take place on a time scale of tens of picoseconds. Collective interactions between the PNA moieties in the multichromphoric arrays results in a marked blue shift in the first absorption maximum from 384 nm for 1-PNA to 375 nm for 2-PNA and to 354 nm for 3-PNA.

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Section: Introductionmentioning

confidence: 99%

Dipolar Triplet States ofp-Nitroaniline andN-Alkyl Derivatives with One-, Two-, and Three-Fold Symmetry

Schuddeboom¹,

Warman²,

Biemans³

et al. 1996

J. Phys. Chem.

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“…It is typical to model an octupole with a twofold degenerate excited state. [18] This degeneracy can be understood by considering a basis in which the charge is placed on one of the three branches of the octupole as shown schematically in Figure 1. With no charge hopping, the states |1 , |2 , and |3 are the three eigenstates of the system.…”

Section: A Sum Rules and The Dipole-free Sos Expressionsmentioning

confidence: 99%

Experimental verification of a self-consistent theory of the first-, second-, and third-order (non)linear optical response

et al. 2011

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We show that a combination of linear absorption spectroscopy, hyper-Rayleigh scattering, and a theoretical analysis using sum rules to reduce the size of the parameter space leads to a prediction of the two-photon absorption cross-section of the dye AF455 that agrees with two-photon absorption spectroscopy. Our procedure, which demands self-consistency between several measurement techniques and does not use adjustable parameters, provides a means for determining transition moments between the dominant excited states based strictly on experimental characterization. This is made possible by our new approach that uses sum rules and molecular symmetry to rigorously reduce the number of required physical quantities.

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“…Molecular nonlinearities in multipolar media have been analyzed using irreducible, spherical representations for β, an approach which provides insight into the shape-dependence of the first hyperpolarizability, particularly with respect to certain symmetry groups 49,50 . For fully symmetric Cartesian tensors, β has a vector (J = 1) and a septor (J = 3) component 51 .…”

Section: Calculation Of Optical Nonlinearities Of Quantum Graphsmentioning

confidence: 99%

Dressed Quantum Graphs With Optical Nonlinearities Approaching the Fundamental Limit

Lytel

Kuzyk

2013

J. Nonlinear Optic. Phys. Mat.

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We dress bare quantum graphs with finite delta function potentials and calculate optical nonlinearities that are found to match the fundamental limits set by potential optimization. We show that structures whose first hyperpolarizability is near the maximum are well described by only three states, the so-called three-level Ansatz, while structures with the largest second hyperpolarizability require four states. We analyze a very large set of configurations for graphs with quasi-quadratic energy spectra and show how they exhibit better response than bare graphs through exquisite optimization of the shape of the eigenfunctions enabled by the existence of the finite potentials. We also discover an exception to the universal scaling properties of the three-level model parameters and trace it to the observation that a greater number of levels are required to satisfy the sum rules even when the three-level Ansatz is satisfied and the first hyperpolarizability is at its maximum value, as specified by potential optimization. This exception in the universal scaling properties of nonlinear optical structures at the limit is traced to the discontinuity in the gradient of the eigenfunctions at the location of the delta potential. This is the first time that dressed quantum graphs have been devised and solved for their nonlinear response, and it is the first analytical model of a confined dynamic system with a simple potential energy that achieves the fundamental limits.

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Second order optical nonlinearity in octupolar aromatic systems

Abstract: We investigate the second-order nonlinear optical properties of octupolar molecules, as opposed to traditional charge transfer dipolar molecules. We consider in particular the case of hexasubstituted aromatic rings, trianiline, trinitrobenzene, and tri-amino-,tri-nitrobenzene (TATB).

Cited by 202 publications

References 12 publications

Dipolar Triplet States ofp-Nitroaniline andN-Alkyl Derivatives with One-, Two-, and Three-Fold Symmetry

Dipolar Triplet States ofp-Nitroaniline andN-Alkyl Derivatives with One-, Two-, and Three-Fold Symmetry

Experimental verification of a self-consistent theory of the first-, second-, and third-order (non)linear optical response

Dressed Quantum Graphs With Optical Nonlinearities Approaching the Fundamental Limit

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