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Electronic States (electronic + states)
Kinds of Electronic States Selected AbstractsWater-Vapor-Induced Reversible Switching of Electronic States in an MMX-Type Chain Complex with Retention of Single Crystallinity,ANGEWANDTE CHEMIE, Issue 3 2010Hiroaki Iguchi Eine reversible Strukturänderung und Änderungen der physikalischen Eigenschaften eines zweikernigen Quasi-1D-Pt-Komplexes werden durch De- und Rehydratisierung ausgelöst. Beim Dehydratisieren geht der elektronische Zustand von einem ACP+CDW- (ACP: alternierende Ladungspolarisierung, CDW: Ladungsdichtewellen) in einen CDW-Zustand mit enger Lücke über, wobei die elektrische Leitfähigkeit und die molare Spinsuszeptibilität bei Raumtemperatur zunehmen. [source] ChemInform Abstract: Low-Lying Electronic States of M3O9 - and M3O92- (M: Mo, W)CHEMINFORM, Issue 3 2008Shenggang Li 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 of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] The Structures and Electronic States of Zinc,Water Clusters Znn(H2O)m (n = 1,32 and m = 1,3)CHEMINFORM, Issue 40 2007Hiroto Tachikawa 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] On the Electronic States of S4+ and S4 - Isomers.CHEMINFORM, Issue 23 2007Hanka Sormova 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] Electronic States and Spectroscopic Properties of SiTe and SiTe+CHEMINFORM, Issue 5 2007Surya Chattopadhyaya 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: Electronic States of Al3P2, Al2P3, and Their Ions.CHEMINFORM, Issue 8 2002K. Balasubramanian 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] Electronic Studies on Oligothienylenevinylenes: Understanding the Nature of Their Ground and Excited Electronic StatesCHEMPHYSCHEM, Issue 11 2009Rocío Ponce Ortiz Abstract The electronic and molecular structures of a family of oligothienylenevinylenes for organic solar cells are studied by means of UV/Vis, fluorescence and Raman spectroscopy, aided by quantum chemical calculations. By using different anchoring groups, the alteration of the electronic properties upon inserting electron-withdrawing groups into different positions on the oligothienylenevinylene backbone is determined. In addition, a thorough study of the photophysical properties is carried out to understand their potential use in optoelectronic devices. The charge defect of one of these systems is analysed to elucidate the possible charge carriers photogenerated during device operation. [source] Density functional theory analysis of a mixed-ligand iridium compound for multi-color organic light-emitting diodesJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 4 2008Silviu Polosan Abstract Electronic states and their energies are calculated for a mixed-ligand Ir(III) compound, (5-chloro-8-hydroxyquinoline) bis(2-phenylpyridyl) iridium (called IrQ(ppy)2 -5Cl) using time-dependent density functional theory (TDDFT) calculations and are compared with the experimental result. A good agreement is obtained between the calculated and measured absorption spectra. The d-,Q* molecular orbital transition gives the lowest-energy triplet state absorption band. Its energy is estimated as 1.84,eV (671,nm), which is close to the absorption band position of 1.86,eV (666,nm) observed for IrQ(ppy)2 -5Cl doped in 4,4,- N,N,-dicarbazole-biphenyl (CBP) host and of 1.88,eV (660,nm) observed for IrQ(ppy)2 -5Cl doped in polystyrene (PS). The second triplet state absorption band is caused by d-,ppy transition. Its position is calculated as 2.51,eV (494,nm). The dipole moment is estimated as 3.45,D, which is lower than the dipole moment of fac -Ir(ppy)3. This is understood by a reduced charge transfer between Ir(III) and quinoline ligand. Copyright © 2008 John Wiley & Sons, Ltd. [source] Electronic states in Cu2MnX (X = Al, In and Sn) Heusler alloy studied by XMCD and multiple scattering calculationsJOURNAL OF SYNCHROTRON RADIATION, Issue 2 2001Shigeaki Uemura X-ray magnetic circular dichroism (XMCD) has been measured at Mn and Cu K-edge in Cu2MnX (X = Al, In, and Sn) Heusler alloy. The Mn K -edge spectrum shows a dispersion-type profile and the Cu K -edge resembles the Mn spectrum, which suggests that polarization of the p unoccupied bands originates commonly in Mn 3d states. To reproduce the observed spectrum by full multiple scattering calculations, Madelung potential has been taken into account. Charge redistribution is an important factor for the electronic structure in Cu2MnX Heusler alloy. [source] Spins as probes of different electronic statesCONCEPTS IN MAGNETIC RESONANCE, Issue 2 2007Dieter Suter Abstract Nuclear spins are efficient probes of electronic states. Because most NMR experiments are performed in thermal equilibrium, they probe the electronic ground state,the only state that is significantly populated under ambient conditions. Probing electronically excited states becomes possible, if magnetic resonance techniques are combined with optical (laser) excitation. Depending on the nature of the electronic state, drastic changes of the magnetic resonance parameters may be observed. We discuss the basic principles of this type of investigation. Depending on the lifetime of the electronically excited state, it is possible to measure separate spectra of ground and excited state if the lifetime is long on the NMR timescale, or an averaged spectrum if the lifetime is short. We present examples for both limiting cases using rare earth ions and semiconductor heterostructures. © 2007 Wiley Periodicals, Inc. Concepts Magn Reson Part A 30A: 116,126, 2007. [source] Control of Solid-State Dye-Sensitized Solar Cell Performance by Block-Copolymer-Directed TiO2 SynthesisADVANCED FUNCTIONAL MATERIALS, Issue 11 2010Pablo Docampo Abstract Hybrid dye-sensitized solar cells are typically composed of mesoporous titania (TiO2), light-harvesting dyes, and organic molecular hole-transporters. Correctly matching the electronic properties of the materials is critical to ensure efficient device operation. In this study, TiO2 is synthesized in a well-defined morphological confinement that arises from the self-assembly of a diblock copolymer,poly(isoprene- b -ethylene oxide) (PI- b -PEO). The crystallization environment, tuned by the inorganic (TiO2 mass) to organic (polymer) ratio, is shown to be a decisive factor in determining the distribution of sub-bandgap electronic states and the associated electronic function in solid-state dye-sensitized solar cells. Interestingly, the tuning of the sub-bandgap states does not appear to strongly influence the charge transport and recombination in the devices. However, increasing the depth and breadth of the density of sub-bandgap states correlates well with an increase in photocurrent generation, suggesting that a high density of these sub-bandgap states is critical for efficient photo-induced electron transfer and charge separation. [source] Application of the anharmonic coherent states to the vibronic interactionFORTSCHRITTE DER PHYSIK/PROGRESS OF PHYSICS, Issue 2-3 2003C.N. Avram We calculated the vibronic reduction factor (Ham factor) for the physical system (molecules, crystals) with octahedral symmetry. The vibrations of the nuclei of the systems are described by the anharmonic states of the Morse potential and also by the anharmonic coherent states of the same potential. The linear vibronic coupling of these vibration states with the electronic states of the system are considered. [source] High-Density Carrier Accumulation in ZnO Field-Effect Transistors Gated by Electric Double Layers of Ionic LiquidsADVANCED FUNCTIONAL MATERIALS, Issue 7 2009Hongtao Yuan Abstract Very recently, electric-field-induced superconductivity in an insulator was realized by tuning charge carrier to a high density level (1,×,1014 cm,2). To increase the maximum attainable carrier density for electrostatic tuning of electronic states in semiconductor field-effect transistors is a hot issue but a big challenge. Here, ultrahigh density carrier accumulation is reported, in particular at low temperature, in a ZnO field-effect transistor gated by electric double layers of ionic liquid (IL). This transistor, called an electric double layer transistor (EDLT), is found to exhibit very high transconductance and an ultrahigh carrier density in a fast, reversible, and reproducible manner. The room temperature capacitance of EDLTs is found to be as large as 34,µF cm,2, deduced from Hall-effect measurements, and is mainly responsible for the carrier density modulation in a very wide range. Importantly, the IL dielectric, with a supercooling property, is found to have charge-accumulation capability even at low temperatures, reaching an ultrahigh carrier density of 8×1014 cm,2 at 220,K and maintaining a density of 5.5×1014 cm,2 at 1.8,K. This high carrier density of EDLTs is of great importance not only in practical device applications but also in fundamental research; for example, in the search for novel electronic phenomena, such as superconductivity, in oxide systems. [source] One-Step Preparation of Coaxial CdS,ZnS and Cd1,xZnxS,ZnS Nanowires,ADVANCED FUNCTIONAL MATERIALS, Issue 8 2005Y.-J. Hsu Abstract Preparation of coaxial (core,shell) CdS,ZnS and Cd1,xZnxS,ZnS nanowires has been achieved via a one-step metal,organic chemical vapor deposition (MOCVD) process with co-fed single-source precursors of CdS and ZnS. Single-source precursors of CdS and ZnS of sufficient reactivity difference were prepared and paired up to form coaxial nanostructures in a one-step process. The sequential growth of ZnS on CdS nanowires was also conducted to demonstrate the necessity and advantages of the precursor co-feeding practice for the formation of well-defined coaxial nanostructures. The coaxial nanostructure was characterized and confirmed by high-resolution transmission electron microscopy and corresponding energy dispersive X-ray spectrometry analyses. The photoluminescence efficiencies of the resulting coaxial CdS,ZnS and Cd1,xZnxS,ZnS nanowires were significantly enhanced compared to those of the plain CdS and plain Cd1,xZnxS nanowires, respectively, owing to the effective passivation of the surface electronic states of the core materials by the ZnS shell. [source] On the electronic structure and bonding of the intriguing mixed Fe2+/Fe3+ [{Cp(CO)2Fe}tBuPO2FeCl2]2 -Complex,HETEROATOM CHEMISTRY, Issue 5 2005Ingo-Peter Lorenz The structure and bonding of [{Cp(CO)2Fe}tBuPO2FeCl2]2(2) have been investigated theoretically and experimentally. The molecular orbitals of 2 have been calculated to investigate the question why this type of complex forms a planar ring system. The electronic configuration of different electronic states, spin polarization, and bonding of 2 are discussed. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:398,405, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20109 [source] Chemical surface passivation of 3C-SiC nanocrystals: A first-principle studyINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 13 2010A. Trejo Abstract The effect of the chemical surface passivation, with hydrogen atoms, on the energy band gap of porous cubic silicon carbide (PSiC) was investigated. The pores are modeled by means of the supercell technique, in which columns of Si and/or C atoms are removed along the [001] direction. Within this supercell model, morphology effects can be analyzed in detail. The electronic band structure is performed using the density functional theory based on the generalized gradient approximation. Two types of pores are studied: C-rich and Si-rich pores surface. The enlargement of energy band gap is greater in the C-rich than Si-rich pores surface. This supercell model emphasizes the interconnection between 3C-SiC nanocrystals, delocalizing the electronic states. However, the results show a clear quantum confinement signature, which is contrasted with that of nanowire systems. The calculation shows a significant response to changes in surface passivation with hydrogen. The chemical tuning of the band gap opens the possibility plenty applications in nanotechnology. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2455,2461, 2010 [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] DFT study for the heterojunction effect in the precious metal clustersINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 15 2008Mitsutaka Okumura Abstract In the case of the precious metal catalysts, the precious metal nanoparticles deposited on the several supports exhibit extremely high-catalytic activity for many catalytic reactions. The boundary region between the nanoparticles and the support is one of the active sites in these catalysts. Moreover, the core/shell-type bimetallic nanoparticles also show the high-catalytic activities for several catalytic reactions. In these systems, the electronic states of the surfaces in the clusters are modified by the heterojunction between the two different compositions. Therefore, we investigate the heterojunction effect in these model catalysts, such as precious metal core/shell clusters and Pd supported on single-wall carbon nanotube model cluster, using hybrid density functional theory. From the calculation results, we find that the charge transfer interactions and the variation of the ground spin states in the metal clusters are the characteristics induced by the heterojunction in these model systems. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] The electronic and optical properties of oligo(trans -1,2-di(2-thienyl)-1,3-butadiene): A theoretical studyINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 13 2008Nei Marçal Abstract In the present work we investigated the theoretical electronic structure of poly(trans -1,4-di(2-thienyl)-1,3-butadiene) (PTB) and determined the optical properties of its neutral and doped oligomers. Geometrical optimizations were at the semiempirical level by using the Austin method 1 (AM1). The band structure of , electrons regarding to the neutral PTB polymer was obtained by using a tight-binding Hamiltonian. The densities of electronic states (DOS) for neutral and doped copolymers were calculated by using the negative factor counting technique. The spatial charge distribution of the oligomeric chain was also analyzed. The energy of the electronic transitions and their associated oscillator strength values were calculated for the neutral, double, and single charged oligomers to determine the UV,vis absorption spectra. The calculations were performed using the intermediate neglect of differential overlap Hamiltonian in combination with the single configuration-interaction technique in order to include correlation effects. The band gap obtained in the PTB was about 2.101 eV for the optics absorption and 1.73 eV for the DOS. The bipolaron states appear in the gap, about 0.57 eV and 0.48 eV below and above the conduction and valence bands, respectively. When the dopants concentration is increased the DOS showed that the energy gap tends to vanish, which may lead to semiconductor,metal transition. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Nonlinear wave function expansions: A progress reportINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 15 2007Ron Shepard Abstract Some recent progress is reported for a novel nonlinear expansion form for electronic wave functions. This expansion form is based on spin eigenfunctions using the Graphical Unitary Group Approach and the wave function is expanded in a basis of product functions, allowing application to closed and open shell systems and to ground and excited electronic states. Each product basis function is itself a multiconfigurational expansion that depends on a relatively small number of nonlinear parameters called arc factors. Efficient recursive procedures for the computation of reduced one- and two-particle density matrices, overlap matrix elements, and Hamiltonian matrix elements result in a very efficient computational procedure that is applicable to very large configuration state function (CSF) expansions. A new energy-based optimization approach is presented based on product function splitting and variational recombination. Convergence of both valence correlation energy and dynamical correlation energy with respect to the product function basis dimension is examined. A wave function analysis approach suitable for very large CSF expansions is presented based on Shavitt graph node density and arc density. Some new closed-form expressions for various Shavitt Graph and Auxiliary Pair Graph statistics are presented. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] Absorption, resonance, and near-resonance Raman studies of the tetracyanoquinodimethane neutral and its monoanion in terms of density functional theory and complete active space self-consistent field methodsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 8 2006Marcin Makowski Abstract The electronic structure of the 11B1u and 12B3u excited electronic states of the tetracyanoquinodimethane (TCNQ) neutral and its charged derivative are studied within the framework of complete active space self-consistent field (CASSCF) and Becke's three-parameter hybrid method with Lee,Yang,Parr correlation functional (B3LYP) methods applied to the level aug-cc-p-VDZ basis set. Both CASSCF/aug-cc-p-VDZ and B3LYP/aug-cc-p-VDZ treatments provide the ground-state and the excited state geometries; these are then used to assess the Franck,Condon (FC) parameters in the 11B1u state of the neutral TCNQ and in the 12B3u state of the TCNQ monoanion. The quality of numerical results is then tested on the base of available experimental near-resonance and resonance Raman data. The studies are performed in terms of the vibronic model, which takes both FC and mode-mixing (Dushinsky) effects into account. This somewhat simplified vibronic model leads to very good agreement between the theory and the Raman experiments concerning both neutral TCNQ and its monoanion. In particular, the calculated excitation profiles of the ,2 = 2215 cm,1, ,4 = 1389 cm,1, ,5 = 1195 cm,1, and ,9 = 336 cm,1 fundamentals are shown to be in excellent agreement with those for the TCNQ monoanion. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] CASSCF study into the mechanism for predissociation of the allyl radicalINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2006Milena Shahu Abstract A theoretical study has been carried out on the allyl radical in its ground and first excited electronic states. Complete active space self-consistent field (CASSCF) calculations show the presence of a conical intersection between the ground and first excited electronic states (,400 cm,1 above the adiabatic excited state energy), reached by decreasing the CCC angle and twisting the CC bonds. The presence of this conical intersection provides a likely explanation for the very rapid predissociation in the excited electronic state. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] Nonadiabatic evolution of electronic states by electron nuclear dynamics theoryINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2005Frank Hagelberg Abstract The problem of how to determine the nonadiabatic content of any given dynamic process involving molecular motion is addressed in the context of Electron Nuclear Dynamics (END) theory. Specifically, it is proposed to cast the dynamic END wave function into the language of static electronic configurations with time dependent complex-valued amplitudes. This is achieved by adiabatic transport of an electronic basis along the classical nuclear trajectories of the studied molecular system, as yielded by END simulation. Projecting the dynamic wave function on this basis yields a natural distinction between adiabatic and nonadiabatic components of the motion considered. Tracing the evolution of the leading configurations is shown to be a helpful device for clarifying the physical nature of electronic excitation processes. For illustration of these concepts, dynamic configuration analysis is applied to the scattering of a proton by a lithium atom. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source] Convenient expression of the rate constant for nonadiabatic transitionINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 1 2005Yoshishige Okuno Abstract We derived a convenient expression of the rate constant for nonadiabatic transitions, with the intention of making it possible and practical to calculate the rate constant. For this derivation, we first assume that the seam, at which the adiabatic potential energy surfaces of reactant and product electronic states exhibit an avoided crossing, corresponds to the dividing surface of the nonadiabatic transition. Second, we use the probability that a nonadiabatic transition occurs in the seam. Third, the partition function in the seam is described by the local profile of the adiabatic potential energy surfaces of both the reactant and product electronic states. The rate constant expression thus derived not only gives significant insight into understanding nonadiabatic transitions, but also makes it possible to obtain a rough estimate of the rate constant. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source] Theoretical studies on high-valent manganese porphyrins: Toward a deeper understanding of the energetics, electron distributions, and structural features of the reactive intermediates of enzymatic and synthetic manganese-catalyzed oxidative processesISRAEL JOURNAL OF CHEMISTRY, Issue 1 2000Abhik Ghosh We present here a relatively comprehensive theoretical study, based on nonlocal density functional theory calculations, of the energetics, electron distributions, and structural features of the low-lying electronic states of various high-valent intermediates of manganese porphyrins. Two classes of molecules have been examined: (a) compounds with the general formula [(P)MnX2]0 (P = porphyrin; X = F, Cl, PF6) and (b) high-valent manganese-oxo species. For [(P)Mn(PF6)2]0, the calculations reveal a number of nearly equienergetic quartet and sextet states as the lowest states, consistent with experimental results on a comparable species, [(TMP)Mn(ClO4)2]0 (TMP = tetramesitylporphyrin). In contrast, [(P)MnCl2]0 and [(P)MnF2]0 have a single well-defined S = 3/2 Mn(IV) ground state, again in agreement with experiment, with the three unpaired spins largely concentrated (>90%) on the manganese atom. Manganese(IV)-oxo porphyrins have an S = 3/2 ground state, with the three unpaired spins distributed approximately 2.3:0.7 between the manganese and oxygen atoms. The metal-to-oxygen spin delocalization, as measured by the oxygen spin population, for MnIV = O porphyrins is less than, but still qualitatively similar to, that in analogous iron(IV)-oxo intermediates, indicating that the MnIV = O bond is significantly weaker than the FeIV = O bond in an analogous molecule. Thus, the optimized metal,oxygen bond distances are 1.654 and 1.674 Å for (P)FeIV(O)(Py) and (P)MnIV(O)(Py), respectively (Py = pyridine). This is consistent with the experimental observation that MnIV = O stretching frequencies are over 10% lower than FeIV = O stretching frequencies for analogous compounds. For [(P)Mn(O)(PF6)]0, [(P)Mn(O)(Py)]+, and [(P)Mn(O)(F)]0, the ground states clearly correspond to a (dxy)2 Mn(V) configuration and the short Mn,O distances of 1.541, 1.546, and 1.561 Å for the three compounds, respectively, reflect the formal triple bond character of the Mn,O interaction. Interestingly, the corresponding Mn(IV)-oxo porphyrin cation radical states are calculated to be a few tenths of an electrovolt higher than the Mn(V) ground states, suggesting that the Mn(IV)-oxo porphyrin cation radicals are not likely to exist as ground-state species. [source] Time-dependent density functional theory study on the electronic excited-state geometric structure, infrared spectra, and hydrogen bonding of a doubly hydrogen-bonded complexJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 16 2009Yufang Liu Abstract The geometric structures and infrared (IR) spectra in the electronically excited state of a novel doubly hydrogen-bonded complex formed by fluorenone and alcohols, which has been observed by IR spectra in experimental study, are investigated by the time-dependent density functional theory (TDDFT) method. The geometric structures and IR spectra in both ground state and the S1 state of this doubly hydrogen-bonded FN-2MeOH complex are calculated using the DFT and TDDFT methods, respectively. Two intermolecular hydrogen bonds are formed between FN and methanol molecules in the doubly hydrogen-bonded FN-2MeOH complex. Moreover, the formation of the second intermolecular hydrogen bond can make the first intermolecular hydrogen bond become slightly weak. Furthermore, it is confirmed that the spectral shoulder at around 1700 cm,1 observed in the IR spectra should be assigned as the doubly hydrogen-bonded FN-2MeOH complex from our calculated results. The electronic excited-state hydrogen bonding dynamics is also studied by monitoring some vibraitonal modes related to the formation of hydrogen bonds in different electronic states. As a result, both the two intermolecular hydrogen bonds are significantly strengthened in the S1 state of the doubly hydrogen-bonded FN-2MeOH complex. The hydrogen bond strengthening in the electronically excited state is similar to the previous study on the singly hydrogen-bonded FN-MeOH complex and play important role on the photophysics of fluorenone in solutions. © 2009 Wiley Periodicals, Inc. J Comput Chem 2009 [source] A combined ab initio and Franck-Condon factor simulation study on the photodetachment spectrum of ScO2,JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 3 2009Edmond P. F. Lee Abstract Restricted-spin coupled-cluster single-double plus perturbative triple excitation {RCCSD(T)} potential energy functions (PEFs) of the 2B2 state of ScO2 and the 1A1 state of ScO2, were computed, employing the augmented correlation-consistent polarized-weighted core-valence quadruple-zeta (aug-cc-pwCVQZ) basis set for Sc and augmented correlation-consistent polarized valence quadruple-zeta (aug-cc-pVQZ) basis set for O, and with the outer core Sc 3s23p6 electrons being explicitly correlated. Franck-Condon factors, which include allowance for Duschinsky rotation and anharmonicity, were calculated using the computed RCCSD(T) PEFs, and were used to simulate the first photodetachment band of ScO2,. The simulated spectrum matches well with the corresponding experimental 355 nm photodetachment spectrum of Wu and Wang, J Phys Chem A 1998, 102, 9129, confirming the assignment of the photodetachment spectrum and the reliability of the RCCSD(T) PEFs used. Further calculations on low-lying electronic states of ScO2 gave adiabatic relative electronic energies (Te's) of, and vertical excitation energies (Tv's) to, the 2A1, 2B1, and 2A2 states of ScO2 (from the 2B2 state of ScO2), as well as electron affinities (EAs) and vertical detachment energies (VDEs) to these neutral states from the 1A1 state of ScO2,. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009 [source] Equivalent potential of water molecules for electronic structure of glutamic acidJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 11 2007Tian Zhang Abstract The fundamental importance of the electronic structure of molecules is widely recognized. To get reliable electronic structure of protein in aqueous solution, it is necessary to construct a simple, easy-use equivalent potential of water molecules for protein's electronic structure calculation. Here, the first-principles, all-electron, ab initio calculations have been performed to construct the equivalent potential of water molecules for the electronic structure of glutamic acid, which is a hydrophilic amino acid and is negatively charged (Glu,) in neutral water solution. The main process of calculation consists of three steps. Firstly, the geometric structure of the cluster containing Glu, and water molecules is calculated by free cluster calculation. Then, based on the geometric structure, the electronic structure of Glu, with the potential of water molecules is calculated using the self-consistent cluster-embedding method. Finally, the electronic structure of Glu, with the potential of dipoles is calculated. Our calculations show that the major effect of water molecules on Glu,'s electronic structure is lowering the occupied electronic states by about 0.017 Ry, and broadening energy gap by 12%. The effect of water molecules on the electronic structure of Glu, can be well simulated by dipoles potential. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007 [source] A theoretical investigation of the excited states of OCLO radical, cation, and anion using the CASSCF/CASPT2 methodJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 2 2007Zi-Zhang Wei Abstract Using the complete active space self-consistent field method with a large atomic natural orbital basis set, 10, 13, and 9 electronic states of the OClO radical, OClO+ cation, and OClO, anion were calculated, respectively. Taking the further correlation effects into account, the second-order perturbation (CASPT2) calculations were carried out for the energetic calibration. The photoelectron spectroscopy of the OClO radical and OClO, anion were extensively studied in the both case of the adiabatic and vertical ionization energies. The calculated results presented the relatively complete assignment of the photoelectron bands of the experiments for OClO and its anion. Furthermore, the Rydberg states of the OClO radical were investigated by using multiconfigurational CASPT2 (MS-CASPT2) theory under the basis set of large atomic natural orbital functions augmented with an adapted 1s1p1d Rydberg functions that have specially been built for this study. Sixteen Rydberg states were obtained and the results were consistent with the experimental results. © 2006 Wiley Periodicals, Inc. J Comput Chem 28: 467,477, 2007 [source] Photochemistry of CH3Mn(CO)5: A multiconfigurational ab initio studyJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 15 2006Leticia González Abstract The electronic spectroscopy of CH3Mn(CO)5 has been investigated by means of ab initio multiconfigurational MS-CASPT2/CASSCF calculations. The absorption spectrum is characterized by a series of Metal-Centered (MC) excited states in the UV energy domain (below 290 nm) that could be responsible for the observed photoreactivity starting at 308 nm. The upper part of the spectrum is overcrowded between 264 and 206 nm and dominated by a high density of Metal-to-Ligand-Charge-Transfer (MLCT) states corresponding mainly to 3dMn , ,*CO excitations. A non-negligible contribution of Metal-to-,-Bond-Charge-Transfer (MSBCT) states corresponding to 3dMn , ,*Mn-CH3 excitations is also present in the theoretical spectrum of CH3Mn(CO)5. However, in contrast to other transition metal hydrides and methyl substituted (HMn(CO)5, HCo(CO)4, and CH3Co(CO)4) these MSBCT transitions do not participate to the lowest bands of the spectrum as main contributions. The photochemistry of CH3Mn(CO)5, namely the loss of a CO ligand vs. the metal-methyl bond homolysis, is investigated by means of MS-CASPT2 states correlation diagrams. This study illustrates the complexity of the photodissociation mechanism of this class of molecules, which involves a large number of nearly degenerate electronic states with several channels for fragmentation. © 2006 Wiley Periodicals, Inc. J Comput Chem, 2006 [source] | ||||||||||||||||||||||||||||||||||