First hyperpolarizability of bacteriorhodopsin, retinal and related molecules revisited

The previously reported beta values of BR and retinal based chromophores were very high but subsequent measurements found them to be much less. We have found that the beta values of these compounds do not vary so much with experimental conditions as with the method of analysis. Hyper-Rayleigh scattering measurements at 1543 and 1907 nm produce more realistic beta values close to the intrinsic (static) hyperpolarizability, beta(0) which for BR is still very high (275 x 10 (30) esu). The optical nonlinearity of BR arises entirely due to the protonated retinal Schiff Base (PRSB) which in its isolated form has the same intrinsic hyperpolarizability as that of the rotein.

Size dependence and dispersion behavior of the first hyperpolarizability of copper nanoparticles

We have probed the size dependency of the first hyperpolarizability (b) of copper nanoparticles by hyper-Rayleigh scattering (HRS). Our results indicate that second harmonic generation (SHG) originates predominantly at the surface of the nanoparticles as long as the size (d) remains small compared to the wavelength (k). However, volume contribution to the SH response due to the retardation effect becomes important when particle size grows beyond the `small particle limit'. There is a significant dispersion in the b values of copper nanoparticles owing tothe presence of the strong surface plasmon resonance (SPR) band.

Base Triggered Enhancement of First Hyperpolarizability of a Keto-Enol Tautomer

This work describes the base triggered enhancement of first hyperpolarizability of a tautomeric organic molecule, namely, benzoylacetanilide (BA). We have used the hyper-Rayleigh scattering technique to measure the first hyperpolarizability (beta) of BA which exists in the pure keto form in water and as a keto-enol tautomer in ethanol. Its anion exists in equilibrium with the keto and enol forms at pH 11 in aqueous solution. The beta value of the anion form is 709 X 10(-30) esu, whereas that of the enol is 232 x 10(-3) esu and of the keto is 88 X 10(-30) esu. There is an enhancement of beta by similar to 8 times for the anion and similar to 3 times for the enol compared to the keto form. All these are achieved by altering the equilibrium between the three forms of BA by simple means. MP2 calculations reproduce the experimental trend, but the computed beta values are much lower than the measured values. DFT calculations with the standard B3LYP functional could not predict the right order in the beta values. The difference between experimental and calculated values is, perhaps, due to the fact that electron correlation effects are important in computing optical nonlinearities of large organic molecules and MP2 and B3LYP calculations done here for different forms of BA could not account for such effects adequately.

First hyperpolarizability of Ru-half-sandwich complexes: The effect of halogen atom substitution on the ancillary ligand

The first hyperpolarizability (beta) of a series of half-sandwich Ru complexes with a mercaptobenzothiazole ligand bearing a halogen atom substitution in the para-position has been investigated by hyper-Rayleigh scattering and quantum chemical calculations. The heterocyclic ligand with a bromine atom in the para position makes it a very good donor and charge flows to the Ru center enhancing the beta value of the complex by a factor of 2 compared to the complex with the ligand without the halogen substitution. The resonance (+R) and the inductive (-I) effects exerted by the halogen atom in the para position push electrons in opposing directions in the complex. For the Br and Cl atoms the resonance effect dominates which enables the ligand to donate electrons to the metal center thereby increasing the hyperpolarizability whereas for the fluorine atom, the inductive effect is dominant which reduces the charge flow to the metal and the hyperpolarizability drops even below that of the unsubstituted ligand. This unprecedented halogen atom effect on beta of metal complexes is reported. (C) 2015 Elsevier By. All rights reserved.

Electronic and vibrational contributions to first hyperpolarizability of donor-acceptor-substituted azobenzene

In this study we report on the electronic and vibrational (hyper)polarizabilities of donor–acceptorsubstituted azobenzene. It is observed that both electronic and vibrational contributions to the electric dipole first hyperpolarizability of investigated photoactive molecule substantially depend on the conformation. The contributions to the nuclear relaxation first hyperpolarizability are found to be quite important in the case of two considered isomers (cis and trans). Although the double-harmonic term is found to be the largest in terms of magnitude, it is shown that the total value of the nuclear relaxation contribution to vibrational first hyperpolarizability is a result of subtle interplay of higher-order contributions. As a part of the study, we also assess the performance of long-range-corrected density functional theory in determining vibrational contributions to electric dipole (hyper)polarizabilities. In most cases, the applied long-range-corrected exchange correlation potentials amend the drawbacks of their conventional counterparts

Experimental and theoretical investigation of first hyperpolarizability in aminophenols

This work reports theoretical and experimental studies on the first hyperpolarizability (beta) of aminophenols, evaluating the influence of the NH(2) group position relative to the OH group on the hyperpolarizability. A new extension of hyper-Rayleigh scattering technique using picosecond pulse trains was employed to obtain the experimental absolute values of (beta). The theoretical static beta(0) values were calculated using AMI method implemented in the AMPAC program. The theoretical and experimental data show a clear dependence between beta and the relative position of the electron donor (D) and acceptor (A) groups, presenting the 2-aminophenol the higher values. Moreover, calculations show excellent qualitative agreement between theoretical and experimental data, which are improved when the simulations considering the solvated molecule in a combination of discrete solvent molecules interacting with the solute and the application of continuous dielectric model. Besides, the study indicates that the experimental hyperpolarizabilities seem to be a property of the solute-solvation shell system. These facts have affirmed that the theoretical approach employed can be successfully used to foresee the variation in beta due to modifications in the D/A position. Moreover, a theoretical study of the ground state absorption is performed and compared with experimental data. (C) 2008 Elsevier B.V. All rights reserved.

Dissociation constants of weak organic acids in protic solvents obtained from their first hyperpolarizabilities in solution

The first hyperpolarizabilities (beta) of some weak aromatic organic acids have been measured in protic solvents by the hyper-Rayleigh scattering (HRS) technique at low concentrations. The measured hyperpolarizability (beta(m)) varies between the two extreme limits: the hyperpolarizability of the acid form (beta(HA)) at the lower side and that of the basic form (beta(A-)) at the higher side. The degree of dissociation (alpha) of the acid in a solvent is related to the measured hyperpolarizability, beta(m), by the following relationship: beta(m)(2)=(1-alpha)beta(HA)(2)+alpha beta(A-)(2). The calculated beta's including solvent effects in terms of an Onsager field do not reproduce the experimentally measured hyperpolarizabilities. Other solvent-induced effects like hydrogen bonding and van der Waals interactions seem to influence the first hyperpolarizability and, thus, indirectly the extent of dissociation of these weak acids in these protic solvents.

Study of the spectroscopic properties and first hyperpolarizabilities of disperse azo dyes derived from 2-amino-5-nitrothiazole

The solvatochromism and other spectroscopic and photophysical characteristics of four azo disperse dyes, derived from 2-amino-5-nitrothiazole, were evaluated and interpreted with the aid of experimental data and quantum mechanical calculations. For the non-substituted compound two conformers, E and Z, were proposed for the isolated molecules, being the second one considerably less stable. The optimization of these structures in combination with a SCRF methodology (IEFPCM, Simulating the molecules in a continuum dielectric with characteristics of methanol), suggests that the Z form is not stable in solution. This same behaviour is expected for the substituted compounds, which is corroborated by experimental data presented in previous investigations [A.E.H. Machado, L.M. Rodrigues, S. Gupta, A.M.F. Oliveira-Campos, A.M.S. Silva, J. Mol. Struct. 738 (2005) 239-245]. For the substituted compounds, two forms derived from E conformer (A and R) are possible. Quantum mechanical data suggest for the isolated molecules, that the low energy absorption hand of the E conformers involve at least two close electronic states. having the low-lying excited state a (1)(n,pi*) nature, and being the S-2 state attributed to a (1)(pi,pi*) transition. The data also suggest a small energy gap between the absorption peaks of A and B, related to the easy conversion between these forms. For the structures optimized in combination with the applied SCRF methodology, an states inversion is observed for the Substituted compounds, with a considerable diminish of the energy gap between A and B absorption peaks. The electronic spectra of these compounds are quite sensitive to changes in the solvent polarity. The positive solvatochromism is more evident in aprotic solvents, probably due to the polarization induced by the solute. These compounds do not fluoresce at 298 K, but present a small but perceptible fluorescence at 77 K, which seems to be favoured by the nature of the group in the 2 `-position of the phenyl ring. Moreover, such compounds present expressive values for first hyperpolarizability, which implies in good non-linear optics (NLO) responses and photoswitching capability. (C) 2008 Elsevier B.V. All rights reserved.

Ferrocene in conjugation with a Fischer carbene: Synthesis, NLO, and electrochemical behavior of a novel organometallic push-pull system

Using an iterative sequence of Wittig olefination, reduction, oxidation, and condensation of an active methylene group to carbonyl, it was possible to prepare a series of organometallic push-pull molecules [(CO)(5)M=C(OCH3)(-CH=CH-)(n)(C5H4)Fe(C5H5), M = W, Cr, n = 1-4] in which ferrocene is the donor element and a Fisher carbene moeity is the acceptor group. The molecular first hyperpolarizability beta was determined by hyper-Rayleigh scattering experiments. The beta values ranged from 110 x 10(-30) to 2420 x 10(-30) esu in acetonitrile, and they are among the highest reported for organometallic molecules so far. Electrochemical measurements are consistent with the push-pull nature of these compounds.

Quadratic Nonlinearity of One- and Two-Electron Oxidized Metalloporphyrins and Their Switching in Solution

We report the quadratic nonlinearity of one- and two-electron oxidation products of the first series of transition metal complexes of meso-tetraphenylporphyrin (TPP). Among many MTPP complexes, only CuTPP and ZnTPP show reversible oxidation/reduction cycles as seen from cyclic voltammetry experiments. While centrosymmetric neutral metalloporphyrins have zero first hyperpolarizability, β, as expected, the cation radicals and dications of CuTPP and ZnTPP have very high β values. The one- and two-electron oxidation of the MTPPs leads to symmetry-breaking of the metal−porphyrin core, resulting in a large β value that is perhaps aided in part by contributions from the two-photon resonance enhancement. The calculated static first hyperpolarizabilities, β0, which are evaluated in the framework of density functional theory by a coupled perturbed Hartree−Fock method, support the experimental trend. The switching of optical nonlinearity has been achieved between the neutral and the one-electron oxidation products but not between the one- and the two-electron oxidation products since dications that are electrochemically reversible are unstable due to the formation of stable isoporphyrins in the presence of nucleophiles such as halides.

Geometry and quadratic nonlinearity of charge transfer complexes in solution using depolarized hyper-Rayleigh scattering

We report large quadratic nonlinearity in a series of 1:1 molecular complexes between methyl substituted benzene donors and quinone acceptors in solution. The first hyperpolarizability, beta(HRS), which is very small for the individual components, becomes large by intermolecular charge transfer (CT) interaction between the donor and the acceptor in the complex. In addition, we have investigated the geometry of these CT complexes in solution using polarization resolved hyper-Rayleigh scattering (HRS). Using linearly (electric field vector along X direction) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D = I-2 omega,I-X,I-X/I-2 omega,I-Z,I-X and D' = I-2 omega,I-X,I-C/I-2 omega,I-Z,I-C in the laboratory fixed XYZ frame by detecting the second harmonic scattered light in a polarization resolved fashion. The experimentally obtained first hyperpolarizability, beta(HRS), and the value of macroscopic depolarization ratios, D and D', are then matched with the theoretically deduced values from single and double configuration interaction calculations performed using the Zerner's intermediate neglect of differential overlap self-consistent reaction field technique. In solution, since several geometries are possible, we have carried out calculations by rotating the acceptor moiety around three different axes keeping the donor molecule fixed at an optimized geometry. These rotations give us the theoretical beta(HRS), D and D' values as a function of the geometry of the complex. The calculated beta(HRS), D, and D' values that closely match with the experimental values, give the dominant equilibrium geometry in solution. All the CT complexes between methyl benzenes and chloranil or 1,2-dichloro-4,5-dicyano-p-benzoquinone investigated here are found to have a slipped parallel stacking of the donors and the acceptors. Furthermore, the geometries are staggered and in some pairs, a twist angle as high as 30 degrees is observed. Thus, we have demonstrated in this paper that the polarization resolved HRS technique along with theoretical calculations can unravel the geometry of CT complexes in solution. (C) 2011 American Institute of Physics. doi:10.1063/1.3514922]

Aryl monosulphides and symmetrical disulphides based second order nonlinear optical chromophores with transparency in the visible

A series of aryl monosulphides and disulphides have been synthesized and characterized. Their molecular hyperpolarizability (beta) has been measured in solution with the hyper-Rayleigh Scattering technique and also calculated by semiempirical AMI method. The trend in the observed and calculated values of first hyperpolarizability of these compounds has been found to be in good agreement. These compounds show moderate P values and excellent transparency in the visible region.

Unsymmetrical aryl disulfides with excellent transparency in the visible region for second order nonlinear optics

Several unsymmetrically substituted aromatic donor acceptor disulfides have been synthesized and analysed for their second order nonlinear optical properties. These molecules exhibit moderately high first hyperpolarizability (beta) with excellent transparency in the visible region. Most of the unsymmetrical disulfides have a cut-off wavelength below 420 nm. Calculations show that the molecules have an asymmetric charge distribution around the disulfide bond which is responsible for their high beta values. These results provide motivation for the design and synthesis of nonlinear optical chromophores with multiple disulfide bonds for large second order nonlinearity and excellent visible transparency.

Linear and nonlinear optical studies on 3,6-bis (2 pyridyl) pyridazine

3,6-Bis (2 pyridyl) pyridazine has been synthesized and characterized by NMR, XRD and elemental analyses. The vibrational studies were carried out by using FTIR and Raman spectroscopy and the modes of vibrations were analysed and compared with the theoretically calculated values. The nonlinear optical property of the title compound was examined by Kurtz-Perry method and Hyper Raleigh scattering with the fundamental wavelength of 1064nm. This compound possesses less SHG efficiency but large first hyperpolarizability. (C) 2013 Elsevier GmbH. All rights reserved.

A new strategy of enhancing two-photon absorption in benzothiazole-containing fluorene molecules: Introduction of auxiliary donor-acceptor effects

A series of benzothiazole-containing fluorene molecules have been designed and their one- and two-photon absorption properties have been investigated theoretically by using the ZINDO method. The effects of electron-excessive/deficient heterocyclic bridges as auxiliary donors (auxD)/acceptors (auxA) on TPA cross-sections were studied. The results show that the molecules with D-pi-auxA-A, D-aux D-pi-A, or D-auxD-pi-auxA-A structure types have large TPA cross-section, which can be a valuable strategy in the design of two-photon absorption materials. Also, a linear relationship between the first hyperpolarizability and the TPA cross-section is observed. (c) 2006 Elsevier B.V. All rights reserved.