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Solution Spectra (solution + spectrum)
Selected AbstractsQM/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] Vibrational spectra of the layered monofluorophosphate (V), NH4Ag3(PO3F)2JOURNAL OF RAMAN SPECTROSCOPY, Issue 11 2009Enrique J. Baran Abstract The powder Fourier-transform (FT) infrared (IR) and Raman spectra of the recently characterized NH4Ag3(PO3F)2 were recorded and are discussed with a site-symmetry analysis based on its known structural data. Some comparisons are made with the solution spectra of the PO3F2, anion and with those of crystalline Ag2PO3F. Copyright © 2009 John Wiley & Sons, Ltd. [source] The Heteropolytungstate Core {BW13O46}11, Derived as Monomer, Dimer, and TrimerCHEMISTRY - A EUROPEAN JOURNAL, Issue 25 2007Nathalie Leclerc-Laronze Dr. Abstract A study of the borotungstate system has led to the characterization of new, original compounds based on the unconventional Keggin derivative [H3BW13O46]8, ion (denoted as 1). [H3BW14O48]6, (2) and the dimer [H6B2W26O90]12, (3) crystallize as mixed cesium/ammonium salts and have been characterized by single-crystal X-ray diffraction analysis. Anion 2 reveals an unusual arrangement, consisting of an outer {W3O9} core grafted onto the monovacant [BW11O39]9, Keggin moiety and exhibits an unprecedented distorted square-pyramidal arrangement for a cis -{WO2} core. Elemental analysis, supported by bond distance analysis, is consistent with the presence of three protons distributed over the terminal oxygens of the outer {W3O7} capping fragment. The [H6B2W26O90]12, ion (3) is formally derived from the direct condensation of two [H3BW13O46]8, subunits. The cisoid arrangement of the two [BW11O39]9, subunits, coupled with the antiparallel arrangement of the two quasi-linear OW,,,OWOH2 chains within the central {W4O12} connecting group, breaks any symmetry, thereby resulting in a chiral compound. Polarography and pH-metric titrations reveal the formation of the monomeric precursor [H3BW13O46]8, (anion 1) under stoichiometric conditions. 183W NMR analysis of 2 and 3 in solution gives complex spectra, consistent with the presence of equilibria between several species. In the frame of this study, we also report on a structural re-investigation of the [H6B3W39O132]15, ion (4) based on reliable results obtained in the solid state by means of single-crystal X-ray diffraction analysis, and in solution by means of 1D and 2D COSY 183W NMR. X-ray diffraction analysis revealed the presence of three attached aquo ligands on the central {W6O15} connecting core, generating three OW,,,OWOH2 quasi-linear chains, which are responsible for the chirality of the trimeric assembly. This structural arrangement accounts for the 39-line 183W solution spectrum. The 2D COSY spectrum permits reliable assignments of the six strongly shielded resonances (around ,250 and ,400,ppm) to the six central W atoms, as well as additional assignments. The origin of such strong shielding for these particular W atoms is discussed on the basis of previously published results. Infrared data for compounds 1, 3, and 4 are also presented. [source] Interaction of Cytidine 5,-Monophosphate with Au(111): An In Situ Infrared Spectroscopic StudyCHEMPHYSCHEM, Issue 9-10 2009Thomas Doneux Dr. Abstract Attracted to gold: The interaction of cytidine 5,-monophosphate (CMP) with gold surfaces is studied at the Au(111) | aqueous solution interface. In situ infrared spectroscopy studies show that cytidine 5,-monophosphate is chemisorbed on Au(111) through the N3 atom of the pyrimidine ring (see picture). The interaction of cytidine 5,-monophosphate (CMP) with gold surfaces is studied by means of in situ infrared spectroscopy and cyclic voltammetry at the Au(111) | aqueous solution interface. Similar to other nucleic acid components, cytidine 5,-monophosphate is chemisorbed on the surface at positive potentials, and the amount of adsorbed CMP increases with the potential. Subtractively normalized interfacial Fourier-transform infrared spectroscopy (SNIFTIRS) is used to identify the adsorbed and desorbed species. Upon electrochemical desorption, the molecules released in solution are unprotonated on the N3 atom. Striking similarities are found between the spectrum of adsorbed CMP and the solution spectrum of protonated CMP. The origin of such similarities is discussed. The results strongly suggest that chemisorption occurs through the N3 atom of the pyrimidine ring. A comparison is drawn with cytidine, whose electrochemical and spectroscopic behaviors are also investigated. 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