Mono(Eta(5)-cyclopentadienyl)metal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies, and first hyperpolarizabilities

A series of mono(eta(5)-cyclopentadienyl)metal-(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(eta(5)-C5H5)(L)(C C{C4H2S}(n)NO2)] (M = Fe, L = kappa(2)-DPPE, n = 1,2; M = Ru, L = kappa(2)-DPPE, 2 PPh3, n = 1, 2; M = Ni, L = PPh3, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV-Vis spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push pull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push pull systems.

Proceedings of the 2nd International Conference on Applied Innovations in IT

This volume contains publications of the 2nd International Conference on Applied Innovations in IT (ICAIIT), which took place in Koethen March 27th 2014. The conference is devoted to problems of applied research in the fields of automation and communications. The research results can be of interest for researchers and development engineers, who deal with theoretical base and the application of the knowledge in the respective areas.

2nd Annual CIBPA Awards for Excellence, 2002

A certificate award from the Canadian Italian Business and Professional Association of Niagara. Mr. Ziraldo is presented with the Business Excellence award on October 26, 2002. The certificate is signed by Walt Lastewka, M.P. Caucus Advocate for SME's.

Plan of levels of marsh land on the line of the proposed ditch from Lyons Creek Culvert on the Welland Canal to lot no. 32 in the 2nd concession of Wainfleet

Plan of levels of marsh land on the line of the proposed ditch from Lyons Creek Culvert on the Welland Canal to lot no. 32 in the 2nd concession of Wainfleet (1 page, hand drawn), n.d.

Certificate that Joseph Kingsmill, sheriff, has sold 7 acres in Lot no. 24 in the 2nd Concession of Caistor to W. H. Dickson

Certificate that Joseph Kingsmill, sheriff, has sold 7 acres in Lot no. 24 in the 2nd Concession of Caistor to W. H. Dickson, May 23, 1857.

Methodology for measuring the impact of mobile technology change from 2nd to 3th generation percerved by users of smes in Barranquilla

This article presents the results of a research project undertaken to obtain a Masters inBusiness Administration from the Business School at the Universidad del Norte, whosepurpose was to identify and test a methodology to measure the impact exerted by thechange from 2nd to 3rd generation mobile tech, based on the perception of users belongingto Barranquilla SME, motivated by the influence of technological changes in behavior andthe knowledge creation among society members, and the importance it has taken to thesurvival of organizations the adoption of applications for process automation, web-basedapplications, voice, data and video that allow the development of competitive advantages,based on information and creativity for new and better products or services.

Additional compact formulas for vibrational dynamic dipole polarizabilities and hyperpolarizabilities

Compact expressions, complete through second order in electrical and/or mechanical anharmonicity, are given for the dynamic dipole vibrational polarizability and dynamic first and second vibrational hyperpolarizabilities. Certain contributions not previously formulated are now included

Simple finite field method for calculation of static and dynamic vibrational hyperpolarizabilities: curvature contributions

In the static field limit, the vibrational hyperpolarizability consists of two contributions due to: (1) the shift in the equilibrium geometry (known as nuclear relaxation), and (2) the change in the shape of the potential energy surface (known as curvature). Simple finite field methods have previously been developed for evaluating these static field contributions and also for determining the effect of nuclear relaxation on dynamic vibrational hyperpolarizabilities in the infinite frequency approximation. In this paper the finite field approach is extended to include, within the infinite frequency approximation, the effect of curvature on the major dynamic nonlinear optical processes

Finite field treatment of vibrational polarizabilities and hyperpolarizabilities: on the role of the Eckart conditions, their implementation, and their use in characterizing key vibrations

In the finite field (FF) treatment of vibrational polarizabilities and hyperpolarizabilities, the field-free Eckart conditions must be enforced in order to prevent molecular reorientation during geometry optimization. These conditions are implemented for the first time. Our procedure facilities identification of field-induced internal coordinates that make the major contribution to the vibrational properties. Using only two of these coordinates, quantitative accuracy for nuclear relaxation polarizabilities and hyperpolarizabilities is achieved in π-conjugated systems. From these two coordinates a single most efficient natural conjugation coordinate (NCC) can be extracted. The limitations of this one coordinate approach are discussed. It is shown that the Eckart conditions can lead to an isotope effect that is comparable to the isotope effect on zero-point vibrational averaging, but with a different mass-dependence

Determination of vibrational polarizabilities and hyperpolarizabilities using field-induced coordinates

An analytical set of field-induced coordinates is defined and is used to show that the vibrational degrees of freedom required to completely describe nuclear relaxation polarizabilities and hyperpolarizabilities is reduced from 3N-6 to a relatively small number. As this number does not depend upon the size of the molecule, the process provides computational advantages. A method is provided to separate anharmonic contributions from harmonic contributions as well as effective mechanical from electrical anharmonicity. The procedures are illustrated by Hartree-Fock calculations, indicating that anharmonicity can be very important