Absorption Spectroscopy Data (absorption + spectroscopy_data)

Distribution by Scientific Domains

Selected Abstracts

Deconvolution of femtosecond time-resolved spectroscopy data in multivariate curve resolution.

Application to the characterization of ultrafast photo-induced intramolecular proton transfer
Abstract In femtosecond absorption spectroscopy, deconvolution of the measured kinetic traces is still an important issue as photochemical processes that may possess shorter characteristic times than the time resolution of the experiment are usually considered. In this work, we propose to perform deconvolution of the time-dependent concentration profiles extracted from multivariate curve resolution (MCR) applied to spectrokinetic data. The profiles are fitted with a model function including a description of the instrumental response function (IRF) of the experiment. The method combines the potential benefits of soft-modeling data analysis with the ones of hard-modeling for parameter estimation. The potential of the method is demonstrated first analyzing five synthetic data sets for which IRF of different widths are simulated. It is then successfully applied to resolve femtosecond UV-visible transient absorption spectroscopy data investigating the photodynamics of salicylidene aniline, a photochromic molecule of wide interest. Considering a time resolution of 150,fs for the IRF, a characteristic time of 45,fs is recovered for the first step of the photo-induced process which consists of an ultrafast intramolecular proton transfer. Our results also confirm the existence of an intermediate species with a characteristic time of 240,fs. Copyright 2010 John Wiley & Sons, Ltd. [source]

Electronic spectra of [(CH3)2NH2]5Cd2CuCl11 crystals

V. Kapustianik
Abstract The temperature evolution of Cu2+ ion environment in the solid solutions of ((CH3)2NH2)5Cd2CuCl11 is studied on the basis of absorption spectroscopy data. For the detailed analysis of experimental data the special program package Crys Tool 1.0 based on quantum-mechanical models, first of all on the model of normalized spherical harmonics (NSH), has been employed. It has been found that similarly to the crystal of ((CH3)2NH2)5Cd3Cl11 (DMACC) the investigated solid solution contains tetragonally distorted octahedral metal,halogen complexes of two types and the degree of their distortion is changed considerably at the temperatures of phase transitions (PTs). The parameters of crystal field, angular overlap model, as well as the copper,chlorine distances, show continuous changes at T1 = 176 K that should be related to the second-order transition, whereas the jump-like anomalies of the spectral parameters at T2 = 115 K (on cooling) are characteristic of the first-order PTs. Introduction of the copper ions into the structure of the host DMACC crystal induces the shifts of these PTs toward low temperatures by 3.5 and 5 K, respectively. The observed structural changes around T0 = 313 K are connected with a complex co-operative effect involving weakening of the hydrogen bonds and modification of the Jahn,Teller distortion with temperature. ( 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

Exciton,phonon interaction and Raman spectra of [(CH3)2NH2]5Cd2CuCl11 crystals

V. Kapustianik
Abstract Temperature evolution of the exciton,phonon interaction (EPI) in ((CH3)2NH2)5Cd2CuCl11 solid solution was studied on the basis of absorption spectroscopy data. The obtained values of effective phonon energies were compared with the data of Raman spectroscopy. It is shown that the (T) and E, parameters of Urbach's rule show the continuous anomalous change characteristic of the second-order phase transition at T1 = 176 K. The anomalous behaviour of the EPI and other spectral parameters at T0 = 310,315 K was related to the complex co-operative effect involving weakening of the hydrogen bonds and variation of the Jahn,Teller distortion of metal,halogen polyhedra with temperature. This process takes place only within the copper,chlorine sublattice and due to this would be hardly related to the usual phase transition. At the same time, the considered temperature change of the tetragonal distortion of the metal,halogen octahedra is followed by nonfulfillment of Urbach's rule in the temperature range TT0. ( 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

Metallomacrocycles with a Difference: Macrocyclic Complexes with Exocyclic Ruthenium(II)-Containing Domains

Abstract The templated synthesis of organic macrocycles containing rings of up to 96 atoms and three 2,2,-bipyridine (bpy) units is described. Starting with the bpy-centred ligands 5,5,-bis[3-(1,4-dioxahept-6-enylphenyl)]-2,2,-bipyridine and 5,5,-bis[3-(1,4,7-trioxadec-9-enylphenyl)]-2,2,-bipyridine, we have applied Grubbs' methodology to couple the terminal alkene units of the coordinated ligands in [FeL3]2+ complexes. Hydrogenation and demetallation of the iron(II)-containing macrocyclic complexes results in the isolation of large organic macrocycles. The latter bind {Ru(bpy)2} units to give macrocyclic complexes with exocyclic ruthenium(II)-containing domains. The complex [Ru(bpy)2(L)]2+ (isolated as the hexafluorophosphate salt), in which L=5,5,-bis[3-(1,4,7,10-tetraoxatridec-12-enylphenyl)]-2,2,-bipyridine, undergoes intramolecular ring-closing metathesis to yield a macrocycle which retains the exocyclic {Ru(bpy)2} unit. The poly(ethyleneoxy) domains in the latter macrocycle readily scavenge sodium ions, as proven by single-crystal X-ray diffraction and atomic absorption spectroscopy data for the bulk sample. In addition to the new compounds, a series of model complexes have been fully characterized, and representative single-crystal X-ray structural data are presented for iron(II) and ruthenium(II) acyclic and macrocyclic species. [source]