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Excitation Energies (excitation + energy)
Kinds of Excitation Energies Terms modified by Excitation Energies Selected AbstractsAntagonistic Effects of Hydrogen Peroxide and Glutathione on Acclimation to Excess Excitation Energy in ArabidopsisIUBMB LIFE, Issue 1 2000Barbara Karpinska Abstract The redox status of the quinone B (QB) and plastoquinone (PQ) pools plays a key role in the cellular and systemic signalling processes that control acclimatory responses in plants. In this study, we demonstrate the effects of hydrogen peroxide and glutathione on acclimatory responses controlled by redox events in the proximity of the QB-PQ pools. Our results suggest that the chloroplast is a sink for H2O2 and that, paradoxically, high concentrations of H2O2 in the chloroplast protect the photosynthetic apparatus and the plant cell from photoinhibition and photooxidative damage. Excess glutathione, however, caused an effect antagonistic to that observed for high H2O2. An explanation of this apparent paradox and a hypothetical redox-signalling model are suggested. [source] Ab Initio Quantum Chemical Investigation of the First Steps of the Photocycle of Phototropin: A Model Study,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 1 2003Christian Neiß ABSTRACT Phototropin is a blue light,activated photoreceptor that plays a dominant role in the phototropism of plants. The protein contains two subunits that bind flavin mononucleotide (FMN), which are responsible for the initial steps of the light-induced reaction. It has been proposed that the photoexcited flavin molecule adds a cysteine residue of the protein backbone, thus activating autophosphorylation of the enzyme. In this study, the electronic properties of several FMN-related compounds in different charge and spin states are characterized by means of ab initio quantum mechanical calculations. The model compounds serve as idealized model chromophores for phototropism. Reaction energies are estimated for simple model reactions, roughly representing the addition of a cysteine residue to the flavin molecule. Excitation energies were calculated with the help of time-dependent density functional theory. On the basis of these calculations we propose the following mechanism for the addition reaction: (1) after photoexcitation of FMN out of the singlet ground state S0, excited singlet state(s) are populated; these relax to the lowest excited singlet state S1, and subsequently by intersystem crossing FMN in the lowest triplet state, T1 is formed; (2) the triplet easily removes the neutral hydrogen atom from the H,S group of the cysteine residue; and (3) the resulting thio radical is added. [source] A Theoretical Investigation of Substituent Effects on the Absorption and Emission Properties of a Series of Terpyridylplatinum(II) Acetylide ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 10 2005Xiao-Juan Liu Abstract A comprehensive calculational investigation has been carried out on a series of complexes of the type [(terpyridyl-R1)Pt(C,C-R2)], where terpyridyl-R1 is a series of substituted 2,2':6',2"-terpyridyl ligands and C,C-R2 is a series of substituted acetylide ligands. In one series of complexes (I), the energy of the electronic excited state is varied by changing the substituents on the terpyridyl ligand (R1). In a second series of complexes (II), this electronic structure variation is obtained by changing the para substituents (R2) of the acetylide ligand. The effect of varying the substituents on the lowest-energy excited states of the complexes has been assessed by calculating their electronic structures and excitation energies. We anticipated that introduction of electron-withdrawing substituents on the terpyridyl ligand will benefit the LLCT (or MLCT) and prohibit the nonradiative pathways via d-d transitions in these complexes; introduction of electron-donating substituents on the acetylide ligand can also prohibit the nonradiative pathways by increasing the energy gaps between the HOMO,LUMO and d-d transitions. The results also reveal that the lowest-energy excitations of all complexes of series I and IIa,b complexes are dominated by a ,(C,C),,,,*(terp) (LLCT) transition mixed with some energetically d,(Pt),,,terpyridyl (MLCT) transition. However, for the complexes IIc,IId, in which phenyl rings are introduced on the acetylide ligand, the lowest-lying absorptions of IIc and IId are predominately LLCT in character, with less MLCT mixture, due to a lower contribution of the Pt(d) orbital to the HOMO, while for IIe, with a stronger donor on the acetylide, the lowest-lying absorption is completely LLCT in character. The absorption and emission calculations using the TDDFT method are based on the optimized geometries obtained at the B3LYP/LanL2DZ and CIS/LanL2DZ levels, respectively. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [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] 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] Tayloring standard TDDFT approaches for computing UV/Vis transitions in thiocarbonyl chromophoresINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4 2008Julien Preat Abstract We report the development of an accurate computational procedure for the calculation of the n , ,* (,max,1) and , , ,* (,max,2) transitions of a set of thiocarbonyl derivatives. To ensure converged results, all calculations are carried out using the 6-311+G(2df,p) basis set for time-dependent calculations, and the 6-311G(2df,p) for the ground-state geometrical optimization. Starting with two hybrids, PBE0 and B3LYP, the Hartree,Fock exchange percentage (,) used is optimized in order to reach excitation energies that fit experimental data. It turns out that BLYP(,) is the more adequate functional for calibration. For the n , ,* excitation, the optimal , value lies in the 0.10,0.20 interval, whereas for the , , ,* process setting , equal to 0.10 provides the most accurate results. The corresponding mean absolute errors (MAE) are limited to 17 nm for ,max,1, and to 10 nm for ,max,2, allowing a consistent and accurate prediction of both transitions. We also assess the merits of the ZINDO//AM1 scheme and it turns out that the semi-empirical method only provides a poor prediction of the ,max of thiocarbonyl derivatives, especially for the n , ,* transition. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Improving the TDDFT calculation of low-lying excited states for polycyclic aromatic hydrocarbons using the Tamm,Dancoff approximationINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 3 2008Yi-Lei Wang Abstract Full TDDFT combined with the commonly used hybrid functional B3LYP has been known to greatly underestimate the 1La excitation energies of large linear acenes. This has cast doubt on the TDDFT results for the similar 1La -type state in other conjugated ,-systems. Although increasing the amount of Hartree,Fock (HF) exchange energy in the employed functional could improve the excitation energy estimation of the 1La state, it would worsen the results for another lowest-lying excited state,1Lb. Calculations of absorption and emitting energies relative to the 1La states for a series of linear acenes showed that a TDDFT scheme incorporating the Tamm,Dancoff approximation (TDDFT/TDA) could decrease the estimation errors by a factor of about 50%, but keep the levels of 1Lb states almost unchanged. Thus, the TDDFT/TDA scheme gives an overall description for the low-lying excited states of linear acenes significantly better than the full TDDFT does. Furthermore, 16 nonlinear polycyclic aromatic hydrocarbons (PAHs) with various structures were examined to confirm the superiority of the TDDFT/TDA over the full TDDFT in its ability to describe the 1La states for conjugated ,-systems of large size. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Bound D-states of helium atom under Debye screeningINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2007Sabyasachi Kar Abstract We have investigated the 1snd1,3D (3 , n , 7) state energies of helium atom embedded in weakly coupled plasma environments using the Rayleigh,Ritz variational method. The effect of the plasma environment is taken care of using a Debye screening model. A correlated wave function involving exponential expansion has been used to represent correlation between the charge particles. The bound 1snd1,3D (3 , n , 7) state energies of helium for various Debye lengths along with the excitation energies of few singlet and triplet states are reported. Our results are useful references to atomic physics, plasma physics, and astrophysics research communities. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] Application of the equivalent-core calculation to the Cl in core level on condensed SiCl4INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 13 2006G. V. S. Mota Abstract Utilization of the equivalent core may be of great help in the determination of excitation energies for condensed systems. This method presents a small difference in the excitation potential in relation to the experimental values, thus, enabling a better symmetry assignment for the excitations involved in the process. With the help of (Z+1)-core model, we estimated the absorption position and the symmetry for the discrete core-excitation state of the Cl K edge on SiCl4 and were able to understand the process of selective fragmentation for condensed systems with good calculation approximation. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] Density functional crystal orbital study of cyano-substituted poly(para -phenylene-vinylene) and poly(quinoxaline-vinylene)INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 8 2006F. Bartha Abstract We have calculated the optical and electronic properties of several conjugated organic polymers: poly(p -phenylene-vinylene) (PPV) and its derivatives. Cyano substitutions on the phenylene ring: poly(2,5-dicyano- p -phenylene-vinylene) (2,5-DCN-PPV) and on the vinylene linkage: poly(p -phenylene-7(,8)-(di)cyano-vinylene) are considered. In addition, poly(quinoxaline-vinylene) (PQV) is studied. The infinite isolated quasi-1D chains are treated with periodic boundary conditions, using atomic basis sets. In a comparative study of PPV, some issues regarding the selection of the functionals and basis sets are discussed and excitation energies derived from time-dependent and from ordinary methods are compared. It is concluded that for these polymers the calculations are informative at the B3LYP/6-31G** density functional theory (DFT) level. The absolute values might change with improved methods, but the similarity of the polymers suggests that the relative characterization is adequate. Band structures are communicated along with characteristics of the highest occupied and the lowest unoccupied crystal orbitals (HOCO and LUCO). Electron affinities, ionization potentials, valence and conduction bandwidths, and effective masses at the bandgap are given. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] Computational study of titanium (IV) complexes with organic chromophoresINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 6 2006Ivan Kondov Abstract A computational study of small titanium complexes with the chromophores catechol, alizarin, and coumarin 343 is presented. Employing density functional theory (DFT), the ground-state geometries, energies, and harmonic frequencies of the different compounds are calculated. Furthermore, time-dependent DFT and the configuration interaction singles (CIS) method are used to determine excitation energies and excited-state gradients. Based on these results, the character of the excited states as well as electronic-vibrational coupling strengths are analyzed, and the implications for electron-transfer reactions at dye,semiconductor interfaces are discussed. © 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] Time-dependent density functional calculations of the Q-like bands of phenylene-linked free-base and zinc porphyrin dimersINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 3 2001Yoichi Yamaguchi Abstract Time-dependent density functional theory (TDDFT) calculations have been performed on the excitation energies and oscillator strengths of the Q-like bands of three structural isomers of phenylene-linked free-base (FBP) and zinc (ZnP) porphyrin dimers. The TDDFT calculated results on the low-lying excited states of the reference monomers, FBP and ZnP, are in excellent agreement with previously calculated and experimental results. It is found that the 1,3- and 1,4-phenylene-linked dimers have monomerlike Q bands that are slightly red-shifted compared to the monomers and new Q, bands comprised of the cross-linked excitations from the FBP (ZnP) ring to the ZnP (FBP) ring at considerably lower energies than the monomer Q bands. For the 1,2-phenylene-linked dimer, the direct ,,, interaction between porphyrin rings caused by the van der Waals repulsion between them provides strong mixing of the Q, bands with the Q bands, which causes its minimum excitation energy to be red-shifted by 0.05 eV compared to the other isomers. The oscillator strengths of the Q, bands are also unexpectedly found to be as strong as those of the Q bands in the dimers. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem 84: 338,347, 2001 [source] Intramolecular electronic communication in a dimethylaminoazobenzene,fullerene C60 dyad: An experimental and TD-DFT studyJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 6 2010K. Senthil Kumar Abstract An electronically push,pull type dimethylaminoazobenzene,fullerene C60 hybrid was designed and synthesized by tailoring N,N -dimethylaniline as an electron donating auxochrome that intensified charge density on the ,-azonitrogen, and on N -methylfulleropyrrolidine (NMFP) as an electron acceptor at the 4 and 4, positions of the azobenzene moiety, respectively. The absorption and charge transfer behavior of the hybrid donor-bridge-acceptor dyad were studied experimentally and by performing TD-DFT calculations. The TD-DFT predicted charge transfer interactions of the dyad ranging from 747 to 601 nm were experimentally observed in the UV-vis spectra at 721 nm in toluene and dichloromethane. A 149 mV anodic shift in the first reduction potential of the NN group of the dyad in comparison with the model aminoazobenzene derivative further supported the phenomenon. Analysis of the charge transfer band through the orbital picture revealed charge displacement from the n(NN) (nonbonding) and , (NN) type orbitals centered on the donor part to the purely fullerene centered LUMOs and LUMO+n orbitals, delocalized over the entire molecule. The imposed electronic perturbations on the aminoazobenzene moiety upon coupling it with C60 were analyzed by comparing the TD-DFT predicted and experimentally observed electronic transition energies of the dyad with the model compounds, NMFP and (E)-N,N -dimethyl-4-(p-tolyldiazenyl)aniline (AZNME). The n(NN) , ,*(NN) and ,(NN) , ,*(NN) transitions of the dyad were bathochromically shifted with a significant charge transfer character. The shifting of ,(NN) , ,*(NN) excitation energy closer to the n , ,*(NN) in comparison with the model aminoazobenzene emphasized the predominant existence of charge separated quinonoid-like ground state electronic structure. Increasing solvent polarity introduced hyperchromic effect in the ,(NN) , ,*(NN) electronic transition at the expense of transitions involved with benzenic states, and the extent of intensity borrowing was quantified adopting the Gaussian deconvolution method. On a comparative scale, the predicted excitation energies were in reasonable agreement with the observed values, demonstrating the efficiency of TD-DFT in predicting the localized and the charge transfer nature of transitions involved with large electronically asymmetric molecules with HOMO and LUMO centered on different parts of the molecular framework. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 [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] Modified regional self-interaction corrected time-dependent density functional theory for core excited-state calculationsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 16 2009Ayako Nakata Abstract A modified regional self-interaction correction (mRSIC) method is proposed for obtaining accurate core-excitation energies in time-dependent density functional theory (TDDFT) calculations. The mRSIC method is an improvement of the RSIC method (Tsuneda et al. J Comput Chem 2003, 24, 1592). It takes into account the energy contributions from 2s and higher atomic orbitals that the RSIC method neglects. Furthermore, mRSIC improves the poor description for the nuclear-electron cusp of Gaussian basis functions. The mRSIC method was combined with a long-range correction (LC) scheme, which has been proved to give accurate valence-, Rydberg-, and charge transfer (CT)-excitation energies. In so doing, it dramatically improved the accuracy of the calculated core-excitation energies and did not affect the already accurate values of valence-, Rydberg-, and CT-excitation energies produced by the LC functionals. These results mean that the combined scheme is accurate for all excitation energy forms. © 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] A dual-level state-specific time-dependent density-functional theoryJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 8 2008Seiken Tokura Abstract A highly efficient new algorithm for time-dependent density-functional theory (TDDFT) calculations is presented. In this algorithm, a dual-level approach to speed up DFT calculations (Nakajima and Hirao, J Chem Phys 2006, 124, 184108) is combined with a state-specific (SS) algorithm for TDDFT (Chiba et al., Chem Phys Lett 2006, 420, 391). The dual-level SS-TDDFT algorithm was applied to excitation energy calculations of typical small molecules, the Q bands of the chlorophyll A molecule, the charge-transfer energy of the zincbacteriochlorin,bacteriochlorin model system, and the lowest-lying excitation of the circumcoronene molecule. As a result, it was found that the dual-level SS-TDDFT gave correct excitation energies with errors of 0.2,0.3 eV from the standard TDDFT approach, with much lower CPU times for various types of excitation energies of large-scale molecules. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2008 [source] Vertical excitation energies for ribose and deoxyribose nucleosidesJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 11 2007Remmick So Abstract Vertical excitation energies for DNA and RNA nucleosides are determined with electron structure calculations using the time-dependent density functional theory (TDDFT) method at the B3LYP/6-311++G(d,p) level for nucleoside structures optimized at the same level of theory. The excitation energies and state assignments are verified using B3LYP/aug-cc-pVDZ level calculations. The nature of the first four excited states of the nucleosides are studied and compared with those of isolated bases. The lowest n,* and ,,* transitions in the nucleoside remain localized on the aromatic rings of the base moiety. New low-energy n,* and ,,* transitions are introduced in the nucleosides as a result of bonding to the ribose and deoxyribose molecules. The effect on the low-lying excited state transitions of the binding to phosphate groups at the 5,- and 3,,5,-hydroxyl sites of the uracil ribose nucleoside are also studied. Some implications of these calculations on the de-excitation dynamics of nucleic acids are discussed. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007. [source] Computational analyses of singlet,singlet and singlet,triplet transitions in mononuclear gold-capped carbon-rich conjugated complexesJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 12 2005Zexing Cao Abstract Density functional theory and CASSCF calculations have been used to determine equilibrium geometries and vibrational frequencies of metal-capped one-dimensional ,-conjugated complexes (H3P)Au(CC)n(Ph) (n = 1,6), (H3P)Au(CCC6H4)(CCPh), and H3PAu(CCC6H4)CCAuPH3 in their ground states and selected low-lying ,,* excited states. Vertical excitation energies for spin-allowed singlet,singlet and spin-forbidden singlet,triplet transitions determined by the time-dependent density functional theory show good agreement with available experimental observations. Calculations indicate that the lowest energy 3(,,*) excited state is unlikely populated by the direct electronic excitation, while the low-lying singlet and triplet states, slightly higher in energy than the lowest triplet state, are easily accessible by the excitation light used in experiments. A series of radiationless transitions among related excited states yield the lowest 3(,,*) state, which has enough long lifetimes to exhibit its photochemical reactivities. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 1214,1221, 2005 [source] Newly developed basis sets for density functional calculationsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 2 2005S. Chiodo Abstract Optimized contracted Gaussian basis sets of double-zeta valence polarized (DZVP) quality for first-row transition metals are presented. The DZVP functions were optimized using the PWP86 generalized gradient approximation (GGA) functional and the B3LYP hybrid functional. For a careful analysis of the basis sets performance the transition metal atoms and cations excitation energies were calculated and compared with the experimental ones. The calculated values were also compared with those obtained using the previously available DZVP basis sets developed at the local-density functional level. Because the new basis sets work better than the previous ones, possible reasons of this behavior are analyzed. The newly developed basis sets also provide a good estimation of other atomic properties such as ionization energies. © 2004 Wiley Periodicals, Inc. J Comput Chem 26: 175,183, 2005 [source] Intruder state avoidance multireference Møller,Plesset perturbation theoryJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 10 2002Henryk A. Witek Abstract A new perturbation approach is proposed that enhances the low-order, perturbative convergence by modifying the zeroth-order Hamiltonian in a manner that enlarges any small-energy denominators that may otherwise appear in the perturbative expansion. This intruder state avoidance (ISA) method can be used in conjunction with any perturbative approach, but is most applicable to cases where small energy denominators arise from orthogonal-space states,so-called intruder states,that should, under normal circumstances, make a negligible contribution to the target state of interests. This ISA method is used with multireference Møller,Plesset (MRMP) perturbation theory on potential energy curves that are otherwise plagued by singularities when treated with (conventional) MRMP; calculation are performed on the 13, state of O2; and the 21,, 31,, 23,, and 33, states of AgH. This approach is also applied to other calculations where MRMP is influenced by intruder states; calculations are performed on the 3,u state of N2, the 3, state of CO, and the 21A, state of formamide. A number of calculations are also performed to illustrate that this approach has little or no effect on MRMP when intruder states are not present in perturbative calculations; vertical excitation energies are computed for the low-lying states of N2, C2, CO, formamide, and benzene; the adiabatic 1A1,3B1 energy separation in CH2, and the spectroscopic parameters of O2 are also calculated. Vertical excitation energies are also performed on the Q and B bands states of free-base, chlorin, and zinc,chlorin porphyrin, where somewhat larger couplings exists, and,as anticipated,a larger deviation is found between MRMP and ISA-MRMP. © 2002 Wiley Periodicals, Inc. J Comput Chem 10: 957,965, 2002 [source] Quantum Mechanical/Molecular Mechanical Studies on Spectral Tuning Mechanisms of Visual Pigments and Other Photoactive Proteins,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 4 2008Ahmet Altun The protein environments surrounding the retinal tune electronic absorption maximum from 350 to 630 nm. Hybrid quantum mechanical/molecular mechanical (QM/MM) methods can be used in calculating excitation energies of retinal in its native protein environments and in studying the molecular basis of spectral tuning. We hereby review recent QM/MM results on the phototransduction of bovine rhodopsin, bacteriorhodopsin, sensory rhodopsin II, nonretinal photoactive yellow protein and their mutants. [source] Ultraviolet Absorption Spectra of Substituted Phenols: A Computational Study,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 1 2006Lei Zhang ABSTRACT Vertical excitation energies for electronic transitions from the ground state to the first two excited states of phenol, mono- and disubstituted methoxyphenols and methyl-substituted phenols have been characterized with the Time-Dependent Density Functional Theory (TD-DFT), the Complete Active Space Self-Consistent Field method (CASSCF) and the Coupled Cluster with Single and Double Excitations Equation-of-Motion approach (CCSD-EOM) to simulate and interpret experimental ultraviolet absorption spectra. While CASSCF excitation energies for the first two transitions either are grossly overestimated or exhibit a weak correlation with experimental data, both TD-DFT and CCSD-EOM perform very well, reproducing the spectral shifts of both the primary band and secondary band observed upon substitution. The conformational dependence of the calculated excitation energies is generally smaller than the shifts caused by substitution. [source] Theoretical resonant Raman spectra of nanotube (7,0) with point defectsPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 11-12 2009Valentin N. Popov Abstract The Raman spectra of the nanotube (7,0) with point defects (monovacancy, divacancy, and Stone,Wales defect) were simulated in order to derive spectroscopic signatures of defective nanotubes. First, we calculated the electronic band structure and the phonon dispersion of the defective nanotubes using supercells within a non-orthogonal tight-binding model. We found that new optical transitions and Raman-active phonons appeared in comparison with the perfect nanotube. Secondly, we calculated the resonance Raman excitation profile for all Raman-active phonons of the defective nanotubes and simulated their Raman spectra at specific laser excitation energies. The predicted high-intensity Raman lines can be used as spectroscopic signatures of the defective nanotubes. [source] High pressure studies of the radial breathing modes in double-wall carbon nanotubesPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 1 2007J. Arvanitidis Abstract This work focuses on the high pressure Raman study of the radial breathing modes (RBMs) of bundled double-wall carbon nanotubes (DWCNTs) using different excitation energies. The detailed examination of the Raman peaks attributed to the RBMs of the inner and outer tubes comprising the DWCNTs as a function of pressure provides a wealth of information concerning the pressure response of individual nanotubes as well as the inner-outer tube (intratube) interactions. The outer tube acts as a protection shield for the inner tube whereas the latter increase the structural stability of the externals upon pressure application. More importantly, the pressure response of the inner tubes, expressed by the normalized pressure slopes ,i = (1/,i) (,,i /,P) vs. frequency of their RBMs, shows a remarkable grouping in quasi-linear distributions wherein ,i increases with ,. This behavior is explained by assuming that the pressure response of an internal tube is crucially dependent on the intratube spacing and thus the structural characteristics of the encapsulating tube. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Raman intensities of the first optical transitions in carbon nanotubesPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 13 2006H. Telg Abstract We performed resonant Raman spectroscopy on the lowest optical transition ES11 of separated single-walled carbon nanotubes by studying the radial-breathing mode (RBM) spectra for excitation energies between 1.15 and 1.48 eV. We were able to extend the experimental Kataura plot to these energies by adding the ES11 transition energies of 11 nanotube chiralities. We discuss also the relative Raman intensities; they are more similar for different family index , than those of the corresponding transitions of the ES22 [1]. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] First-principles optical spectra of low dimensional systemsPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 15 2005Letizia Chiodo Abstract Low dimensional systems, such as organic molecules, nanotubes, nanowires, have attracted great interest in the last few years, due to their possible application in nanodevices. It is therefore important to describe accurately the electronic excitations, with highly reliable and efficient ab-initio approaches. A standard technique for studying the ground-state properties is the Density Functional Theory; however when electronic excited states are involved, the many-body Green's functions theory is used for obtaining quasi-particle excitation energies and optical spectra. In this paper we will present the current status of this theoretical and computational approach, showing results for a bulk semiconductor and for two different kinds of low dimensional systems. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Electronic structure and transport properties of quantum dotsANNALEN DER PHYSIK, Issue 5 2004M. Tews Abstract The subject of this paper are electronic properties of isolated quantum dots as well as transport properties of quantum dots coupled to two electronic reservoirs. Thereby special focus is put on the effects of Coulomb interaction and possible correlations in the quantum dot states. First, the regime of sequential tunneling to the reservoirs is investigated. It is shown that in case degenerate states participate in transport, the resonance positions in the differential conductance generally depend on temperature and the degree of degeneracy. This effect can be used to directly probe degeneracies in a quantum dot spectrum. A further effect, characteristic for sequential tunneling events, is the complete blocking of individual channels for transport. A generalisation of the well known spin blockade is found for correlated dot states transitions through which are not directly spin-forbidden. In the second part, the electronic structure of spherical quantum dots is calculated. In order to account for correlation effects, the few-particle Schrödinger equation is solved by an exact diagonalization procedure. The calculated electronic structure compares to experimental findings obtained on colloidal semiconductor nanocrystals by Scanning Tunneling Spectroscopy. It is found that the electric field induced by the tunneling tip is gives rise to a Stark effect which can break the spherical symmetry of the electronic ground state density which is in agreement with wave-function mapping experiments. The symmetry breaking depends on the competition between exchange energy and the Stark energy. Moreover, a systematic dependence on particle number is found for the excitation energies of optical transitions which explains recent experimental findings on self-organized quantum dots. In the last part, co-tunneling in the Coulomb blockade regime is studied. For this end the tunneling current is calculated up to the forth order perturbation theory in the tunnel coupling by a real-time Green's function approach for the non-equilibrium case. The differential conductance calculated for a quantum dot containing up to two interacting electrons shows complex signatures of the excitation spectrum which are explained by a combination of co-tunneling and sequential tunneling processes. Thereby the calculations show a peak structure within the Coulomb blockade regime which has also been observed in experiment. [source] Electronic Structure of the Ground and Excited States of ,-CarbolineCHEMPHYSCHEM, Issue 6 2008Vicente Pérez Mondéjar Abstract Coupled-cluster calculations are used to compute the energy of conversion between the neutral and the zwitterionic forms of ,-carboline. The stability of the different species is discussed in terms of charge separation and aromatic character, which is related to magnetic criteria. By means of a linear response formalism the vertical excitation energies and oscillator strengths of the lowest singlet states of both structures as well as of the cationic species are determined. General agreement of the relative position and intensity of the different peaks with experimental data is achieved, but the overall spectra are slightly displaced because of solvent effects. [source] | ||||||||||||||||||||||||||||