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Electronic Spectra (electronic + spectrum)
Selected AbstractsElectronic Spectra and DFT Calculations of Hexanuclear Chalcocyanide Rhenium Clusters.CHEMINFORM, Issue 11 2005S. G. Kozlova Abstract For Abstract see ChemInform Abstract in Full Text. [source] Assignment of the Electronic Spectra of [Mo(CN)8]4- and [W(CN)8]4- by ab initio Calculations.CHEMINFORM, Issue 31 2004M. F. A. Hendrickx No abstract is available for this article. [source] Theoretical Study on the Structures and Electronic Spectra of TCNE2,,CHEMPHYSCHEM, Issue 2 2006Inmaculada García Cuesta Dr. Abstract Investigations into the charge-separated states and electron-transfer transitions in tetracyanoethylene (TCNE) complexes have recently generated much interest. In this work we present theoretical calculations showing that the most stable structure of the dianion TCNE2,has D2dsymmetry in vacuum as well as in the solvents dichloromethane and acetonitrile. By means of the coupled cluster linear response, we compute the vertical electronic spectrum in both the gas phase and solution. The theoretical results are compared to the experimental data and good agreement is achieved. [source] Electronic Spectra of Ti(IV) in Zeolites: An Ab Initio ApproachCHEMPHYSCHEM, Issue 7 2005Ettore Fois Prof. Dr. Charge transfer in Ti,zeolites: Model titanium,zeolites containing a single Ti(IV) tetrahedral species were built and their electronic excitation spectra were calculated (see picture) via time-dependent density functional theory (TDDFT). A multiple-band profile was obtained in each case, thus highlighting that the features observed in the UV/Vis spectra are not a direct evidence of chemically different Ti(IV) sites. [source] A CASPT2 Study of the Electronic Spectrum of Hexacyanoosmate(III).CHEMINFORM, Issue 47 2007Willem Van den Heuvel Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] ChemInform Abstract: A DFT Study of the Electronic Spectrum of the ,-Keggin Anion [CoIIW12O40]6- .CHEMINFORM, Issue 21 2002Joan Miquel Maestre Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Resin-IV: Synthesis and characterization of terpolymers derived from 2-hydroxyacetophenone, melamine, and formaldehydeJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2008R. H. Gupta Abstract Terpolymer resins (2-HAMF) were prepared by the condensation of 2-hydroxyacetophenone and melamine with formaldehyde in the presence of acid catalyst and using varied molar ratios of reacting monomers. Compositions of terpolymers have been determined by elemental analysis. The number average molecular weights (Mn) have been determined by conductometric titration in nonaqueous medium. Viscometric measurements in dimethyl sulfoxide have been carried out with a view to ascertain the characteristic functions and constants. Electronic spectra, infrared and nuclear magnetic resonance spectra were studied to elucidate the structure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] QM/MM calculation of solvent effects on absorption spectra of guanineJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 1 2010Maja Parac Abstract Electronic spectra of guanine in the gas phase and in water were studied by quantum mechanical/molecular mechanical (QM/MM) methods. Geometries for the excited-state calculations were extracted from ground-state molecular dynamics (MD) simulations using the self-consistent-charge density functional tight binding (SCC-DFTB) method for the QM region and the TIP3P force field for the water environment. Theoretical absorption spectra were generated from excitation energies and oscillator strengths calculated for 50 to 500 MD snapshots of guanine in the gas phase (QM) and in solution (QM/MM). The excited-state calculations used time-dependent density functional theory (TDDFT) and the DFT-based multireference configuration interaction (DFT/MRCI) method of Grimme and Waletzke, in combination with two basis sets. Our investigation covered keto-N7H and keto-N9H guanine, with particular focus on solvent effects in the low-energy spectrum of the keto-N9H tautomer. When compared with the vertical excitation energies of gas-phase guanine at the optimized DFT (B3LYP/TZVP) geometry, the maxima in the computed solution spectra are shifted by several tenths of an eV. Three effects contribute: the use of SCC-DFTB-based rather than B3LYP-based geometries in the MD snapshots (red shift of ca. 0.1 eV), explicit inclusion of nuclear motion through the MD snapshots (red shift of ca. 0.1 eV), and intrinsic solvent effects (differences in the absorption maxima in the computed gas-phase and solution spectra, typically ca. 0.1,0.3 eV). A detailed analysis of the results indicates that the intrinsic solvent effects arise both from solvent-induced structural changes and from electrostatic solute,solvent interactions, the latter being dominant. © 2009 Wiley Periodicals, Inc. J Comput Chem 2010 [source] Electronic spectra of [(CH3)2NH2]5Cd2CuCl11 crystalsPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 11 2004V. 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] Electronic spectrum of 2-pyridone+: Ab initio and time-dependent density functional calculationsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 3 2010D. Hammoutène Abstract In a comparative study, the doublet and quartet electronic states of the 2-pyridone+ cation are calculated using the PBE0/6-311+G(d,p) technique and the CASSCF and MRCI(+Q) methods in connection with the cc-pVDZ and cc-pVTZ Dunning's basis sets. Our data show that TD-DFT describes quite well the vertical excitation energies of these electronic states, whereas, multiconfiguration methods should be used for the investigation of the fragmentation and the dynamics of this molecular species. This is related to the change of the nature of the wavefunction of these electronic states along the corresponding reactive coordinates not accounted for by TD-DFT methods. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] 4- and 4,5-Substituted N -Methoxythiazole-2(3H)-thiones , Preparation,UV/Vis Spectra, and Assignment of Electronic Transitions in Comparison to N -Methoxypyridine-2(1H)-thione Using Time-Dependent Density Functional Theory CalculationsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 5 2005Jens Hartung Abstract Experimentally observed absorptions in UV/Vis spectra of N -methoxy-4-methylthiazole-2(3H)-thione, N -methoxy-5-(p -methoxyphenyl)-4-methylthiazole-2(3H)-thione, N -methoxypyridine-2(1H)-thione, and selected N -hydroxy derivatives thereof have been assigned to ,,,*-type transitions as dominating character, using the results from ab initio calculations [time-dependent density functional theory (TD)RI-BLYP/TZVPP]. Theory further predicts that electronic excitations in N -methoxythiazole-2(3H)-thiones on one side and N -meth-oxypyridine-2(1H)-thione on the other side differ significantly with respect to character and statistical weight of contributing transitions. These effects originate predominantly from contributions of the endocyclic sulfur atom onto orbital energies and shapes in thiazole-2(3H)-thiones, and may be intensified by substituents such as a p -methoxyphenyl group located in position 5. Since the majority of the calculated spectral differences between thiazole- and pyridinethiones refers to excitations of low intensity, the findings from the present study correlate with two important experimental facts: (i) Apart from minor shifts in the exact spectral location of UV/Vis absorptions, electronic spectra of N -hydroxy- or N -methoxy-substituted pyridine-2(1H)-thiones and thiazole-2(3H)-thiones are surprisingly similar in shape. (ii) N -alkoxypyridine-2(1H)-thiones and N -alkoxythiazole-2(3H)-thiones liberate upon UV/Vis excitation oxygen-centered radicals with a comparable efficiency. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Photochromic Properties of Perhydro- and Perfluorodithienylcyclopentene Molecular SwitchesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 10 2003Jaap J. D. de Jong Abstract Various substituted phenylthienyl perhydro- and perfluorocyclopentenes have been synthesized in order to compare their spectroscopic and photochromic properties. The difference in the electron densities of the central cyclopentene moieties in the perhydrocyclopentene and perfluorocyclopentene molecular switches has only a small effect on the absorption maxima of the electronic spectra, but causes some subtle changes in substituent and solvatochromic effects. The photochromic behaviour is remarkably similar, and both type of switches combine excellent quantum yields (0.6) with high degrees of photoconversion (> 0.85). The main difference is the lower photochemical and thermal stability of the perhydrocyclopentene molecular switches. It is concluded that in most studies the perhydrocyclopentenes are an excellent alternative for the perfluorocyclopentenes, while the perfluorocyclopentenes might be better suited for applications such as data storage, which depend critically on fatigue resistance and thermal stability. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] A Joint Theoretical and Experimental Insight into the Electronic Structure of Chromophores Derived from 6H,12H -5,11-Methanodibenzo[b,f][1,5]diazocineHELVETICA CHIMICA ACTA, Issue 11 2007Vincent Lemaur Abstract We report on the synthesis and electronic spectra of the chiral, donor-acceptor (push-pull) chromophores (±)- 4 and (±)- 5 with a 6H,12H -5,11-methanodibenzo[b,f][1,5]diazocine scaffold (Scheme,1 and Fig.,2). The electronic structures of these compounds were investigated at a quantum-chemical level (Figs.,2 and 3). The chemical reactivity of 6H,12H -5,11-methanodibenzo[b,f][1,5]diazocine ((±)- 11) towards aromatic electrophilic substitution (Scheme,2 and Table) provided additional information about its electronic structure and confirmed nonnegligible delocalization of the lone pair of the bridge-head N-atoms in this heterocyclic system. [source] Theoretical studies on structures and electronic spectra of linear carbon chains C2nH+ (n = 1,5)INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2009Jinglai Zhang Abstract The density functional theory (DFT) and the complete active space self-consistent-field (CASSCF) method have been used for full geometry optimization of carbon chains C2nH+ (n = 1,5) in their ground states and selected excited states, respectively. Calculations show that C2nH+ (n = 1,5) have stable linear structures with the ground state of X3, for C2H+ or X3,, for other species. The excited-state properties of C2nH+ have been investigated by the multiconfigurational second-order perturbation theory (CASPT2), and predicted vertical excitation energies show good agreement with the available experimental values. On the basis of our calculations, the unsolved observed bands in previous experiments have been interpreted. CASSCF/CASPT2 calculations also have been used to explore the vertical emission energy of selected low-lying states in C2nH+ (n = 1,5). Present results indicate that the predicted vertical excitation and emission energies of C2nH+ have similar size dependences, and they gradually decrease as the chain size increases. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Theoretical electronic spectra of 2-aminopurine in vapor and in waterINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 13 2006Antonio Carlos Borin Abstract The accurate quantum chemical CASSCF and CASPT2 methods combined with a Monte Carlo procedure to mimic solvation effects have been used in the calculation of the spectroscopic properties of two tautomers of 2-aminopurine (2AP). Absorption and emission spectra have been simulated both in vacuum and in aqueous environment. State and transition energies and properties have been obtained with high accuracy, leading to the assignment of the most important spectroscopic features. The lowest-lying 1(,,,*) (1La) state has been determined as responsible for the first band in the absorption spectrum and also for the strong fluorescence observed for the system in water. The combined approach used in the present work gives quantitatively accurate results. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] Thermal, catalytic, antimicrobial, and chelating aspects of phenolic resin and its polychelates with f-block elementsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2008M. M. Patel Abstract The polymeric ligand (resin) was synthesized by condensation of 2-hydroxy-4-ethoxybenzophenone with ethane diol in the presence of polyphosphoric acid as a catalyst at 145°C for 10 h. The synthesized resin was used to study its ion exchange efficiency and to synthesize its polychelates with 4f-block elements. The resin and its polychelates were characterized on the basis of elemental analyses, electronic spectra, magnetic susceptibilities, IR, NMR, and thermogravimetric analyses. The molecular weight was determined using number,average molecular weight (Mn) by a vapor pressure osmometry (VPO) method. Ion-exchange studies at various concentrations of different electrolytes, pH, and rate have been carried out for f-block elements. Antimicrobial activity of all polychelates and catalytic activity of selected polychelates in organic synthesis have been studied. It is observed that resin can be used as an ion-exchanger and polychelates are found to be an efficient catalysts and antimicrobial agents. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Theoretical study of the electronic spectra of oxidized and reduced states of lumiflavin and its derivativeJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 4 2007Yoong-Kee Choe Abstract Time-dependent density functional theory has been applied to investigate the electronic absorption spectrum of oxidized and reduced lumiflavin and its derivative, 8-NH2 -lumiflavin. The calculations allow the authors to explain the origin of the difference in spectral features between oxidized and reduced states of lumiflavin. For the reduced lumiflavin, a reasonable assignment of the experimental spectrum has been made for the first time. Furthermore, the results obtained reveal that the NH2 group plays a critical role in shaping the spectral features of 8-NH2 -lumiflavin, and offer a reasonable explanation for the spectral changes upon substituting the NH2 group for the CH3 group of lumiflavin. © 2007 Wiley Periodicals, Inc. J Comput Chem 28: 727,739, 2007 [source] Study of electronic spectra of free-base porphin and Mg-porphin: Comprehensive comparison of variety of ab initio, DFT, and semiempirical methodsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 3 2005Josef Abstract SAC (symmetry adapted cluster)/SAC-CI and CASPT2 (multiconfigurational second-order perturbation theory) electron excitation spectra of free-base porphin and magnesium-porphin were determined using basis set functions augmented by both the polarization and diffuse functions,6-31+G(d). Such basis is recommended for correct description of the spectra because diffuse functions play fundamental roles in the formation of Rydberg MOs. The obtained results indicated that already the lowest roots in Au, B1u, B2g, and B3g irreducible representations display Rydberg character. The calculated spectra are in a good agreement with both experimental and recently calculated electronic transitions. It is concluded that the SAC/SAC-CI level spectral lines are significantly affected by configuration selection when energy thresholds 5.0 × 10,6 and 5.0 × 10,7 a.u. are used for the determination of ground and excited state properties. © 2004 Wiley Periodicals, Inc. J Comput Chem 26: 294,303, 2005 [source] Raman spectra of a pseudo-oxocarbon anion in ionic liquidsJOURNAL OF RAMAN SPECTROSCOPY, Issue 5 2010Humberto C. Garcia Abstract Raman and electronic spectra of the [3,5-bis(dicyanomethylene)cyclopentane-1,2,4-trionate] dianion, the croconate violet (CV), are reported in solutions of ionic liquids based on imidazolium cations. Different normal modes of the CV anion, , (CO), , (CO) + , (CC) + , (CCN), and ,(C,N), were used as probes of solvation characteristics of ionic liquids, and were compared with spectra of CV in common solvents. The spectra of CV in ionic liquids are similar to those in dichloromethane solution, but distinct from those in protic solvents such as ethanol or water. The UV,vis spectra of CV in ionic liquids strongly suggest ,,, interactions between the CV anion and the imidazolium cation. Copyright © 2009 John Wiley & Sons, Ltd. [source] Nanocarbon materials: probing the curvature and topology effects using phonon spectraJOURNAL OF RAMAN SPECTROSCOPY, Issue 9 2009Sanju Gupta Abstract Much has been learned from the use of resonance Raman spectroscopy and high-resolution transmission electron microscopy techniques about the micro-/nanoscopic structure of various nanostructured carbons. However, they still possess some features that are not entirely understood particularly in terms of topological characteristics, which go beyond making a distinction with just the geometrical structure at nanoscale. To effectively utilize the potential of these materials for technological needs, understanding both the geometrical and topological structure and perhaps relating these attributes to physical (optical/electronic, lattice vibrational) properties become indispensable. Here, we make an attempt to describe the differences between various nanostructures and provide geometrical and topological property assessment semiquantitatively by monitoring the phonon spectra using resonance Raman spectroscopy thereby also capturing the electronic spectra. We elucidate the notion of global topology and curvature for a range of technologically important nanoscale carbons including tubular (single-, double- and multiwalled nanotubes, peapod), spherical (hypo- and hyperfullerenes, onion-like carbon) and complex (nanocones, nanohorns, nanodisks and nanorings) geometries. To demonstrate the proof-of-concept, we determined the variation in the prominent Raman bands of the respective materials, represented as D, G and D* (the overtone of D) bands, as a possible topological or curvature trend due to their sensitivity toward structural modification. The latter arises from local topological defects such as pentagons giving rise to curved nanocarbons. In this study, we provide systematics of their variation with respect to their geometric forms and compare with highly oriented pyrolytic graphite and monolayer graphene since the nanocarbons discussed are their derivatives. Once established, this knowledge will provide a powerful machinery to understand newer nanocarbons and indeed point to an unprecedented emergent paradigm of global topology/curvature , property , functionality relationship. We emphasize that these concepts are applicable to other topologically distinct nanomaterials, which include boron-nitride (BN) nanotubes and nanotori, helical gold nanotubes and Möbius conjugated organics. Copyright © 2009 John Wiley & Sons, Ltd. [source] Syntheses, characterization and biological studies of zinc(II), copper(II) and cobalt(II) complexes with Schiff base ligand derived from 2-hydroxy-1-naphthaldehyde and selenomethionineAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 10 2010Xueguang Ran Abstract Novel zinc(II), copper(II), and cobalt(II) complexes of the Schiff base derived from 2-hydroxy-1-naphthaldehyde and D, L -selenomethionine were synthesized and characterized by elemental analysis, IR, electronic spectra, conductance measurements, magnetic measurements and powder XRD. The analytical data showed the composition of the metal complex to be ML(H2O), where L is the Schiff base ligand and M = Co(II), Cu(II) and Zn(II). IR results confirmed the tridentate binding of the Schiff base ligand involving azomethine nitrogen, naphthol oxygen and carboxylato oxygen atoms. 1H NMR spectral data of lithium salt of the Schiff base ligand [Li(HL)] and ZnL(H2O) agreed with the proposed structures. The conductivity values of complexes between 12.50 and 15.45 S cm2 mol,1 in DMF suggested the presence of non-electrolyte species. The powder XRD studies indicated that Co(II) complex is amorphous, whereas Cu(II) and Zn(II) complexes are crystalline. The results of antibacterial and antifungal screening studies indicated that Li(HL) and its metal complexes are active, but CuL(H2O) is most active among them. Copyright © 2010 John Wiley & Sons, Ltd. [source] Antibacterial, spectral and thermal aspects of drug based-Cu(II) mixed ligand complexesAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 10 2009G. J. Kharadi Abstract The antibiotic agent clioquinol is well known for its drug design and coordinating ability towards metal ions. Copper(II) mixed-ligand complexes of clioquinol with various uninegative bidentate ligands were prepared. The structure of the synthesized complexes was characterized using elemental analyses, infrared spectra, 1H-NMR spectra, electronic spectra, magnetic measurements, FAB mass spectrum and thermo gravimetric analyses. The kinetic parameters such as order of reaction (n) and the energy of activation (Ea) are reported using the Freeman,Carroll method. The pre-exponential factor (A), the activation entropy (,S#), the activation enthalpy (,H#) and the free energy of activation (,G#) were calculated. Complexes were also screened for their in vitro antibacterial activity against a range of Gram-positive and Gram-negative bacteria in order to set the precursors for anti-tumourigenic agent. Copyright © 2009 John Wiley & Sons, Ltd. [source] Conformations and properties of the L -tryptophyl-containing peptides in solution, depending on the pH,Theoretical study vs. experimentsBIOPOLYMERS, Issue 8 2010Bojidarka B. Ivanova Abstract The conformational preference and electronic properties of three L -tryptophyl-containing dipeptides, i.e., glycyl- L -tryptophane (H-Gly-Trp-OH), L -alanyl- L -tryptophane (H-Ala-Trp-OH), and L -methionyl- L -tryptophane (L -Met-Trp-OH) in solution depending on the pH of the media are studied both theoretically and experimentally. The effect of the protonation of the COO, and deprotonation of the NH as well as the alkaline hydrolysis of the amide fragment in a strong basic media on the electronic spectra are discussed. Ab initio and density functional theory (DFT) methods as well as the time-dependent DFT (TD-DFT) method as a function of the basis set are performed with a view to obtain the geometry and electronic properties of all of the species as well as the intermediate, obtained in the alkaline hydrolysis mechanism. © 2010 Wiley Periodicals, Inc. Biopolymers 93: 727,734, 2010. This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com [source] The Low-Lying Excited States of 2,2,-Bithiophene: A Theoretical AnalysisCHEMPHYSCHEM, Issue 12 2003Mercedes Rubio Dr. Abstract The low-energy regions of the singlet,singlet, singlet,triplet, and triplet,triplet electronic spectra of 2,2,-bithiophene are studied using multiconfigurational second-order perturbation theory (CASPT2) and extended atomic natural orbitals (ANO) basis sets. The computed vertical, adiabatic, and emission transition energies are in agreement with the available experimental data. The two lowest singlet excited states, 11Bu and 21Bu, are computed to be degenerate, a novel feature of the system to be borne in mind during the rationalization of its photophysics. As regards the observed high triplet quantum yield of the molecule, it is concluded that the triplet states 23Ag and 23Bu, separated about 0.4 eV from the two lowest singlet excited states, can be populated by intersystem crossing from nonplanar singlet states. [source] Semi-Empirical and DFT Studies on Structures and Spectra for C78(CH2)2CHINESE JOURNAL OF CHEMISTRY, Issue 2 2007Shi Wu Abstract Eighteen possible isomers of C78(CH2)2 were investigated by the INDO method. It was indicated that the most stable isomer was 42,43,62,63-C78(CH2)2, where the ,CH2 groups were added to the 6/6 bonds located at the same hexagon passed by the longest axis of C78 (C2v), to form cyclopropane structures. Based on the most stable four geometries of C78(CH2)2 optimized at B3LYP/3-21G level, the first absorptions in the electronic spectra calculated with the INDO/CIS method and the IR frequencies of the C,C bonds on the carbon cage computed using the AM1 method were blue-shifted compared with those of C78 (C2v) because of the bigger LUMO-HOMO energy gap and the less conjugated carbon cage after the addition. The chemical shifts of 13C NMR for the carbon atoms on the added bonds calculated at B3LYP/3-21G level were moved upfield thanks to the conversion from sp2 -C to sp3 -C. [source] Effect of water on zinc (II), cadmium (II) complexes with pyridylimidazole: Theoretical study of stability and electronic spectrumINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2006Yi Liao Abstract The geometry structures of complexes such as [Zn(PIm)2(H2O)] and [Cd(PIm)2(H2O)2] [PIm = (2-(2,-pyridyl) imidazole)] are optimized by density functional theory (DFT) B3LYP methods. On the basis of their stable structures, the stability of the coordinated water existing in the complexes is analyzed quantitatively in terms of the interaction between the central metal and the coordinated water. The interaction energy of the Zn pyridylimidazole complex increased obviously by considering the intermolecular hydrogen bond (OH,N). The theoretical calculation well explained penta- and hexa-coordinated conformation, respectively, in Zn and Cd pyridylimidazole complexes. The spectral properties of the Zn Cd complexes have been studied by time-dependent density functional theory (TD-DFT). The calculation results show that the coordinated waters in Cd complexes have little effect on their spectral properties. While the axially coordinated waters in Zn pyridylimidazole cause a red shift in the absorption wavelength and change the pattern of charge transfer as a result of the effect of polarization from intermolecular hydrogen bond. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] Temperature effects on the UV,Vis electronic spectrum of trans-stilbeneINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4-5 2001S. P. Kwasniewski Abstract The ultraviolet (UV),Visible absorption spectrum of trans-stilbene (tS) is computed at different temperatures by coupling molecular dynamics (MD) simulations with the classical MM3 force field to ZINDO/S-CIS calculations of vertical excitation energies and transition dipole moments. The selection of a large number of structures along the MD trajectories enables a consistent treatment of temperature effects in the vacuum, whereas the ZINDO/S-CIS calculations permit a reliable treatment of electron correlation and relaxation, taking account of multistate interactions in the final state. Thermal motions are found to alter very differently the width and shape of bands. Structural alterations such as the stretching and the torsion of the vinyl single and double bonds very strongly influence the appearance of the first valence state, pertaining to the highest occupied and lowest unoccupied molecular orbital (HOMO,LUMO) transition. At temperatures less than 400 K, these are found to yield a merely Gaussian and very pronounced thermal broadening of the related band (A), up to nearly 30 nm, together with a minor blue shift of its maximum ,max. In contrast, a red shift by several nanometers occurs due to thermal motions for the remaining three valence bands. As can be expected, the broadening intensifies at higher temperatures, and for the A-band, becomes markedly asymmetric when T exceeds 400 K. The combination of MD(MM3) and ZINDO/S-CIS computations enables also consistent calculations of hot bands, which are forbidden by symmetry at 0 K. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001 [source] Spectroscopic and Electrochemical Evaluation of Salt Effects on Electron-Transfer Equilibria between Donor/Acceptor and Ion-Radical Pairs in Organic SolventsCHEMPHYSCHEM, Issue 16 2008Sergiy V. Rosokha Dr. Abstract Addition of "inert" tetrabutylammonium hexafluorophosphate (Bu4NPF6) to a solution of TMDO/DDQ in dichloromethane (where TMDO=2,2,6,6-tetramethylbenzo[1,2-d;4,5-d]bis[1,3]-dioxole, donor, and DDQ=diclorodicyano-p-benzoquinone, acceptor) is accompanied by drastic changes in the electronic spectrum, which are related to the appearance of the DDQ,. and TMDO+. ion radicals and a decrease in the concentration of the neutral molecules and the charge-transfer complex [TMDO,DDQ]. These changes point to a considerable rise (of about three orders of magnitude) in the apparent electron-transfer equilibrium constant (KET) for this donor/acceptor pair upon increasing the electrolyte concentration from 0 to 0.5,M. Accordingly, the ion-radical fractions and KET values are higher in dichloromethane, at high electrolyte concentrations, than in acetonitrile (where the effect of Bu4NPF6 is less pronounced). Similar trends of the apparent equilibrium constants are observed for the tetramethyl-p-phenylenediamine/tetracyanoethylene pair. Electron-transfer equilibrium constants for both donor/acceptor dyads obtained from spectral measurements are related to those derived from the redox potentials of the reactants. The effects of media variations on the electron-transfer equilibria are discussed within the ion-pairing and ionic-activity frameworks. [source] Spin-Orbit Ab Initio Investigation of the Ultraviolet Photolysis of DiiodomethaneCHEMPHYSCHEM, Issue 6 2007Ya-Jun Liu Dr. Abstract The UV photodissociation (<5 eV) of diiodomethane (CH2I2) is investigated by spin-orbit ab initio calculations. The experimentally observed photodissociation channels in the gas and condensed phases are clearly assigned by multi-state second-order multiconfigurational perturbation theory in conjunction with spin-orbit interaction through complete active space-state interaction potential energy curves. The calculated results indicate that the fast dissociations of the first two singlet states of CH2I2 and CH2II lead to geminate-radical products, CH2I,.+I(2P3/2) or CH2I,.+ I*(2P1/2). The recombination process from CH2II to CH2I2 is explained by an isomerization process and a secondary photodissociation reaction of CH2II. Finally, the study reveals that spin-orbits effects are significant in the quantitative analysis of the electronic spectrum of the CH2II species. [source] Theoretical Study on the Structures and Electronic Spectra of TCNE2,,CHEMPHYSCHEM, Issue 2 2006Inmaculada García Cuesta Dr. Abstract Investigations into the charge-separated states and electron-transfer transitions in tetracyanoethylene (TCNE) complexes have recently generated much interest. In this work we present theoretical calculations showing that the most stable structure of the dianion TCNE2,has D2dsymmetry in vacuum as well as in the solvents dichloromethane and acetonitrile. By means of the coupled cluster linear response, we compute the vertical electronic spectrum in both the gas phase and solution. The theoretical results are compared to the experimental data and good agreement is achieved. [source] | |||||||||||||||||||||||||