Measurements of Nonlinear Light Scattering

Terhune, R. W.; Maker, P. D.; Savage, C. M.

doi:10.1103/physrevlett.14.681

Cited by 574 publications

(329 citation statements)

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“…2 The establishment of detailed structureactivity correlations for first hyperpolarizabilities , which govern quadratic molecular NLO effects, is the primary objective of most current work with such metal-based chromophores. Our contribution to this field has focused on hyper-Rayleigh scattering (HRS) 3 and electronic Stark effect (electroabsorption) 4 spectroscopic studies with various Ru II pyridyl ammine complexes of pyridiniumsubstituted ligands. 5 We have found that such dipolar chromophores can exhibit very large static first hyperpolarizabilities  0 that are associated with intense, low energy metal-to-ligand charge-transfer (MLCT) transitions.…”

Section: Introductionmentioning

confidence: 99%

Syntheses, spectroscopic and molecular quadratic nonlinear optical properties of dipolar ruthenium(ii) complexes of the ligand 1,2-phenylenebis(dimethylarsine)

et al. 2004

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Six new complex salts trans-[Ru II Cl(pdma) 2 L] [PF 6 ] n [pdma = 1,2-phenylenebis(dimethylarsine); L = (E,E,E)-1,6-bis(4-pyridyl)hexa-1,3,5-triene (bph), n = 1, 5; L = N-methyl-4- [(E)-2-(4-pyridyl) -methyl-4-[2-(4-pyridyl)ethynyl]pyridinium (Mebpa + ), n = 2, 11] have been prepared. The electronic absorption spectra of 5 and 7-11 display intense, visible metal-to-ligand charge-transfer (MLCT) bands, with  max values in the range 434-492 nm in acetonitrile. Cyclic voltammetric studies reveal reversible Ru III/II waves with E 1/2 values in the range 1.06-1.15 V vs. Ag-AgCl, together with irreversible L-based reduction processes. Along with a number of previously reported related compounds (B. J. Coe et al., J. Chem. Soc., Dalton Trans., 1996, 3917; 1997, 591; 2000, 797), salts 5 and 7-11 have been investigated by using Stark (electroabsorption) spectroscopy in butyronitrile glasses at 77 K. These studies have afforded dipole moment changes  12 for the MLCT transitions which have been used to calculate molecular static first hyperpolarizabilities  0 according to the two-state equation  0 = 3 12 ( 12 ) 2 /(E max ) 2 ( 12 = transition dipole moment, E max = MLCT energy). MLCT absorption and electrochemical data show that a trans-{Ru II Cl(pdma) 2 } + centre is considerably less electron-rich than a {Ru II (NH 3 ) 5 } 2+ unit. Although the  0 responses of the pdma complexes are only a little smaller than those of their {Ru II (NH 3 ) 5 } 2+ analogues, this result is partly attributable to unexpected changes in the relative  12 values on freezing. Thus, substantial increases in  12 for the arsine compounds act to partially offset the  0 -decreasing influence of their higher E max values when compared with the analogous pentaammine species. Single crystal X-ray structures have been obtained for the salts 1·2.5MeCN, 4·2MeCN, 7 and 11, but only 1·2.5MeCN adopts a non-centrosymmetric space group (Fdd2) such as may show bulk NLO effects.

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Section: Introductionmentioning

confidence: 99%

Syntheses, spectroscopic and molecular quadratic nonlinear optical properties of dipolar ruthenium(ii) complexes of the ligand 1,2-phenylenebis(dimethylarsine)

et al. 2004

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“…Furthermore, subsequent experimental 5 and theoretical 6 work has indicated that the HRS-technique may also be used to determine the values of the other elements of the molecular ␤ i jk tensor, essentially by measuring HRS-depolarization ratios in a series of experiments utilizing both linearly and circularly polarized light. 7 As a result, HRS, first observed in the 1960s, 8 nowadays has developed into an important tool in the nonlinear optics ͑NLO͒ field.…”

Section: Introductionmentioning

confidence: 99%

Molecular simulation of static hyper-Rayleigh scattering: A calculation of the depolarization ratio and the local fields for liquid nitrobenzene

Janssen

Theodorou

Raptis

et al. 1999

The Journal of Chemical Physics

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Papadopoulos, M. G. (1999). Molecular simulation of static hyper-Rayleigh scattering : a calculation of the depolarization ratio and the local fields for liquid nitrobenzene. Journal of Chemical Physics, 111(21), 9711-9719. DOI: 10.1063/1.480305 General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Molecular dynamics ͑MD͒ simulation is used to assess the hyper-Rayleigh scattering ͑HRS͒ depolarization ratio of liquid nitrobenzene subject to vertically polarized light. In contrast to previous theoretical work, we have quantified both incoherent and coherent scattering arising from positional and orientational inhomogeneities in the molecular distribution. Although coherent scattering is shown to be much less important than in the case of Rayleigh scattering, it can not be neglected. Therefore, our analysis supports the current practice of working with dilute solutions ͑for which coherent contributions to HRS are truly negligible͒ to extract the first molecular hyperpolarizability from HRS measurements. In cases where experiments with pure liquids can not be circumvented, our analysis may be used to separate coherent and incoherent signals. Our work, which uses as input static ''gas-phase'' ͑hyper͒polarizabilities obtained from ab initio calculations, also provides information on the orientations and magnitudes of the local electric fields experienced by the individual molecules in the liquid. For nitrobenzene it is found that the local fields are largely determined by specific dipolar alignment between neighboring pairs of molecules, with consequences on the HRS signal.

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“…The incoherent term gives the hyper-Rayleigh contribution (Terhune et al 1965, Kielich et a1 1971, 1974 and corresponds to a relatively weak background scattering in comparison with the total harmonic power. Dropping the incoherent term, and then using the fact that, irrespective of any orientational order, the gross translational invariance of the system ensures that the spatial and orientational factors can be separated, we obtain where the angular brackets denote rotational averaging to allow for the distribution of molecular orientations.…”

Section: Quantum Formalismmentioning

confidence: 99%

Orientational effects in electric-field-induced second-harmonic generation

Andrews

Sherborne

1986

J. Phys. B: At. Mol. Phys.

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Abstract. The theory of electric-field-induced second-harmonic generation is developed within the framework of quantum electrodynamics. Using a recently developed exact averaging procedure to account for the anisotropy introduced to a dipolar molecular fluid by the static electric field, the polarisation dependence of the process is investigated. A number of experimental arrangements are suggested which allow a discrimination to be made between the two mechanisms involved: the third-order optical route facilitated by the field-induced anisotropy, and the fourth-order electro-optical route. This allows measurement of the corresponding non-linear optical and e!ectro-optical tensor parameters. The full temperature and field-strength dependences are presented in detail, and it is shown that in two particular polarisation cases, that of helicity conversion, and where the static field and pump polarisation are perpendicular to the polarisation of the harmonic, the usual approximation for the orientational average is incomplete and produces misleading results.

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Measurements of Nonlinear Light Scattering

Cited by 574 publications

References 5 publications

Syntheses, spectroscopic and molecular quadratic nonlinear optical properties of dipolar ruthenium(ii) complexes of the ligand 1,2-phenylenebis(dimethylarsine)

Syntheses, spectroscopic and molecular quadratic nonlinear optical properties of dipolar ruthenium(ii) complexes of the ligand 1,2-phenylenebis(dimethylarsine)

Molecular simulation of static hyper-Rayleigh scattering: A calculation of the depolarization ratio and the local fields for liquid nitrobenzene

Orientational effects in electric-field-induced second-harmonic generation

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