Quantum and tensorial modeling of multipolar nonlinear optical chromophores by a generalized equivalent internal potential

Abstract

Articles you may be interested inStudy of linear and nonlinear optical properties of dendrimers using density matrix renormalization group method J. Chem. Phys. 131, 074111 (2009); 10.1063/1.3202437 Quantum-chemical investigation of second-order nonlinear optical chromophores: Comparison of strong nitrilebased acceptor end groups and role of auxiliary donors and acceptorsThe equivalent internal field model, originally developed for linear one-dimensional chromophores, is extended to three-dimensional multipolar chromophores. The extension requires two generalizations to the model. First, the equivalent internal field must be generalized to an equivalent internal potential. Second, all tensor components of the hyperpolarizability must be taken into account. A general formalism is developed for analyzing the hyperpolarizabilities induced by application of various internal potentials to a molecular skeleton, assuming the hyperpolarizabilities are linearly related to the internal potential. This formalism utilizes a symmetry analysis, along with quantum chemical calculations done here with the Hückel, Pariser-Parr-Pople and intermediate neglect of differential overlap ͑INDO͒ Hamiltonians and using single-configuration interaction theory. The formalism is applied to and tested on the benzene molecular skeleton. The hyperpolarizability is found to be linearly related to the internal potential provided the potential difference between carbon atoms is below a threshold of the order of 2 eV. Various predictions of the model are tested against explicit INDO and ab initio calculations on mono-substituted, ortho-disubstituted, meta-disubstituted, and tri-substituted benzenes. For the substituents F, CH 3 , OCH 3 , OH, and NH 2 , many of the predictions of the equivalent internal potential model apply, indicating that the internal potentials arising from these substituents are in the linear regime. For the NO 2 and CN substituents, strong effects from nonlinear coupling are observed. The disagreements between the various quantum chemical treatments ͑INDO and various ab initio approaches͒ are largest for molecules exhibiting nonlinear coupling effects, indicating that the nonlinear effects are more difficult to calculate than linear effects. , ͑21͒where the sum is over all J and M . Due to Kleinmann symmetry, 5,7 which is valid away from resonance, only the Jϭ1 and Jϭ3 components are nonzero.

The synthesis of tetrahedral bipyridyl metallo-octupoles with large second- and third-order nonlinear optical properties

“…[37]. Although this model is not valid for 2-or 3-dimensional charge transfer processes [38], it has been shown that in the case of purely octupolar systems, the 3-level dispersion equation is equivalent to the 2-level one owing to the degeneracy of the two excited states [39]. In the case of MLCT additional transition for copper complexes, the weak molar absorption coefficient associated to it makes its contribution to the b values almost negligible.…”

Excitonically Coupled Oligomers and Dendrimers for Two-Photon Absorption

“…Zyss has widely demonstrated the interest of multipolar systems for quadratic NLO [107][108][109]; on the basis of his theory, efficient octupolar quadratic nonlinear systems have been designed [110][111][112][113][114][115][116]. This symmetry has been considered as a new strategy for the design of efficient systems in the field of TPA.…”

Donor-substituted triaryl-1,3,5-triazinanes-2,4,6-triones: octupolar NLO-phores with a remarkable transparency–nonlinearity trade-off

“…The corresponding static hyperpolarizability values b HRS (0) were also derived. 4,16,17 Among the organic compounds 1-X and 2-X, increasing the donating strength of the substituents or the length of the bridge results in an enhancement of b HRS , which is partly attributable to dispersion factors, according to the corresponding b HRS (0) values. The electronic effect of the X substituent on b HRS (0) values appears predominant over the bridge elongation.…”