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Energy Curves (energy + curve)
Kinds of Energy Curves Selected AbstractsEndohedral carbon chains in chiral single-wall carbon nanotubesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 11 2006Ravi K. Vadapalli Abstract Using a first-principles, local density functional approach, we report the bond length optimization of endohedral linear carbon chains. In these calculations, all-carbon nanowire structures were constructed by inserting cumulenic linear carbon chains inside the semiconducting (7,3) and metallic (7,4) single-wall carbon nanotubes with radii of ,0.35 nm. Our calculations show that the total energy results for the endohedral chains inside both (7,3) and (7,4) nanotubes are well described with a common total energy curve having an equilibrium bond length of ,0.129 nm. The electronic band structures of the carbon nanowires are described in terms of a rigid-band model, with the Fermi level for the carbon nanowire effectively pinned near the top of bands originating from the valence band of the single-wall nanotube. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] Energy decomposition scheme for combined ab initio quantum mechanical / molecular mechanical methodsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 3 2005Imre Berente Abstract A new energy decomposition scheme is presented which paves the way toward the accurate and simple treatment of boundary atoms in combined ab initio quantum mechanical / molecular mechanical methods. We extend the wave function beyond the quantum region to a few atoms of the molecular mechanical region, which are linked directly to boundary atoms. Furthermore, we apply an approximate decomposition scheme, which allows calculating the total energy in terms of one-center atomic contributions. Comparisons with reference ab initio calculations are made, and good agreement is obtained for geometry parameters referring to CC, CC, and CX (XO, S, N) bonds at the boundary, as well as for the rotational energy curve of n -butane. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source] Ab initio investigation on the reaction path and rate for the gas-phase reaction of HO + H2O , H2O + OHJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 13 2003Tadafumi Uchimaru Abstract This article describes an ab initio investigation on the potential surfaces for one of the simplest hydrogen atom abstraction reactions, that is, HO + H2O , H2O + OH. In accord with the findings in the previously reported theoretical investigations, two types of the hydrogen-bonding complexes [HOHOH] and [H2OHO] were located on the potential energy surface. The water molecule acts as a hydrogen donor in the [HOHOH] complex, while the OH radical acts as a hydrogen donor in the [H2OHO] complex. The energy evaluations at the MP2(FC) basis set limit, as well as those through the CBS-APNO procedure, have provided estimates for enthalpies of association for these complexes at 298 K as ,2.1 , ,2.3 and ,4.1 , ,4.3 kcal/mol, respectively. The IRC calculations have suggested that the [H2OHO] complex should be located along the reaction coordinate for the hydrogen abstraction. Our best estimate for the classical barrier height for the hydrogen abstraction is 7.8 kcal/mol, which was obtained from the CBS-APNO energy evaluations. After fitting the CBS-APNO potential energy curve to a symmetrical Eckart function, the rate constants were calculated by using the transition state theory including the tunneling correction. Our estimates for the Arrhenius parameters in the temperature region from 300 to 420 K show quite reasonable agreement with the experimentally derived values. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 1538,1548, 2003 [source] Conformational properties of thiophene oligomersJOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 4 2000Salvatore Millefiori The molecular geometries and the torsional potentials about the inter-ring C-C bond in ,-oligothiophenes (,-nTh, n=2,4) have been calculated by means of conventional ab initio and density functional theory (DFT) calculations employing the hybrid B3LYP and BH&HLYP functionals. The position and the energetics of the critical points in the potential energy curve generated by rotation about the inter-ring CC bond are shown to be dependent on the computational method. DFT calculations, in comparison with MP2 calculations, favour conjugative interactions, while steric and coulombic interactions are equally treated by both methods. On oligomerization the electron delocalisation increases slightly, the p-charge being preferentially confined within the rings, although it is sufficient to move the molecular structure towards co-planarization and to increase the barrier through the perpendicular conformation. The IR and Raman spectra on the relevant rotamers of ,-2Th have been computed at HF/6,31G* and B3LYP/6,31G* levels. The comparison with the experiment is excellent. It has been found that small twisting from the planar conformation has no apparent effects, while 90° twisting and isomerization to the syn-gauche form produce significant frequency and intensity variations which could be useful probes in conformational studies. The simulated IR and Raman spectra of the ,-2Th rotamers are consistent with a small,-electron delocalisation between the rings. [source] Exact Fixed-node Quantum Monte Carlo: Differential ApproachCHINESE JOURNAL OF CHEMISTRY, Issue 11 2005Hong-Xin Huang Abstract A differential approach for exact fixed-node quantum Monte Carlo calculation was proposed in this paper. This new algorithm can be used to directly compute the energy differential between two systems in exact fixed-node quantum Monte Carlo process, making the statistical error of calculation reduce to order of 10,2 kJ/mol and recover about more than 90% of the correlation energy. The approach was employed to set up a potential energy surface of a molecule, through a model of rigid move, and Jacobi transformation utilized to make energy calculation for two configurations of a molecule having good positive correlation. So, an accurate energy differential could be obtained, and the potential energy surface with good quality depicted. This novel algorithm was used to study the potential energy curve of the ground state of BH and the potential energy surface of H3, and could be also applied to study other related fields such as molecular spectroscopy and the energy variation of chemical reactions. [source] Interaction of atoms with graphenic-type surfaces for the chemistry of the interstellar medium: New properties of H dimers on the surfaceINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 12 2010D. Teillet-Billy Abstract Following the works of Rougeau et al. (Chem Phys Lett 2006, 431,135) and Ferro et al. (Phys Rev B 2008, 78, 085417) on the one-sided double chemisorption of H atoms on graphenic platelets, we investigate the two-sided double chemisorption using DFT-GGA PW91 calculations. Equilibrium characteristics and potential energy curves for chemisorption are reported for the ortho, meta, para, and bottom positions. Contrary to the one-sided case, the two-sided ortho chemisorption, as well as the bottom position, is barrier-less, whereas the two-sided para chemisorption exhibits an activation barrier. The highest occupied Kohn-Sham orbital (HOKSO) of the H-graphene radical is shown to signal the privileged barrier-less double chemisorption sites. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] Inverse problems in quantum chemistryINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 11 2009Jacek Karwowski Abstract Inverse problems constitute a branch of applied mathematics with well-developed methodology and formalism. A broad family of tasks met in theoretical physics, in civil and mechanical engineering, as well as in various branches of medical and biological sciences has been formulated as specific implementations of the general theory of inverse problems. In this article, it is pointed out that a number of approaches met in quantum chemistry can (and should) be classified as inverse problems. Consequently, the methodology used in these approaches may be enriched by applying ideas and theorems developed within the general field of inverse problems. Several examples, including the RKR method for the construction of potential energy curves, determining parameter values in semiempirical methods, and finding external potentials for which the pertinent Schrödinger equation is exactly solvable, are discussed in detail. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] The chemiionization reactions Ce + O and Ce + O2: Assignment of the observed chemielectron bandsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 10 2009Tanya K. Todorova Abstract Multiconfigurational quantum chemical methods (CASSCF/CASPT2) have been used to study the chemiionization reactions Ce + O , CeO+ + e, and Ce + O2 , CeO + e,. Selected spectroscopic constants for CeOn and CeO (n = 1, 2), as well as reaction enthalpies of the chemiionization reactions of interest, have been computed and compared with experimental values. In contrast to the lanthanum case, for both Ce + O2(X3,) and Ce + O2( a1,g), the Ce + O2 , CeO + e, reaction is shown to be exothermic, and thus, contributes to the experimental chemielectron spectra. The apparent discrepancy between the computed reaction enthalpies and the high kinetic energy offset values measured in the chemielectron spectra is rationalized by arguing that chemielectrons are produced mainly via two sequential reactions (Ce + O2 , CeO + O, followed by Ce + O , CeO+ + e,) as in the case of lanthanum. For Ce + O2 (a1,g), a chemielectron band with higher kinetic energy than that recorded for Ce + O2( X3,) is obtained. This is attributed to production of O( 1D) from the reaction Ce + O2( a1,g) , CeO + O( 1D), followed by chemiionization via the reaction Ce + O( 1D) , CeO+ + e,. Accurate potential energy curves for the ground and a number of excited states of CeO and CeO+ have been computed, and a mechanism for the chemiionization reactions investigated experimentally was proposed. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Grid-based density functional calculations of many-electron systemsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2008Amlan K. RoyArticle first published online: 10 DEC 200 Abstract Exploratory variational pseudopotential density functional calculations are performed for the electronic properties of many-electron systems in the 3D cartesian coordinate grid (CCG). The atom-centered localized gaussian basis set, electronic density, and the two-body potentials are set up in the 3D cubic box. The classical Hartree potential is calculated accurately and efficiently through a Fourier convolution technique. As a first step, simple local density functionals of homogeneous electron gas are used for the exchange-correlation potential, while Hay-Wadt-type effective core potentials are employed to eliminate the core electrons. No auxiliary basis set is invoked. Preliminary illustrative calculations on total energies, individual energy components, eigenvalues, potential energy curves, ionization energies, and atomization energies of a set of 12 molecules show excellent agreement with the corresponding reference values of atom-centered grid as well as the grid-free calculation. Results for three atoms are also given. Combination of CCG and the convolution procedure used for classical Coulomb potential can provide reasonably accurate and reliable results for many-electron systems. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Comparison of charge transfer recombination of (3s2 3p) third row S3+ and P2+ ions with HINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 14 2007M. C. Bacchus-Montabonel Abstract We present a compared dynamical study of the S3+(3s23p)2P° + H and P2+(3s23p)2P° + H collision systems involving an accurate ab initio calculation of the potential energy curves and couplings of the molecular states involved in each process followed by a semi-classical collision treatment in the keV laboratory energy range. The results are in good agreement with experiment, when available, and different mechanisms may be pointed out for these reactions in connection with the different molecular interactions involved. © 2007 Wiley Periodicals, Inc. J Quantum Chem, 2007 [source] Theoretical investigations on analytical potential energy function and spectroscopic parameters for the state b3,u of dimer 7Li2INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 9 2007De-Heng Shi Abstract The SAC-CI (symmetry-adapted-cluster configuration-interaction) method presented in Gaussian 03 program package is applied to investigate the adiabatic potential energy curves (PECs) of 7Li2(b3,u). These calculations are performed at numbers of basis sets, such as 6-311++G(3df,3pd), 6-311++G(2df,2pd), 6-311++G(df,pd), D95V++, D95(3df,3pd), D95(d,p), cc-PVTZ, 6-311++G and 6-311++G(d,p). All the ab initio calculated points are fitted to the analytic Murrell-Sorbie functions and then used to compute the spectroscopic parameters. The analytic potential energy function (APEF) for this b3,u state is reported. By comparison, the spectroscopic parameters reproduced by the APEF attained at 6-311++G(2df,2pd) are found to be very close to the latest experimental findings. With the APEF obtained at the SAC-CI/6-311++G(2df,2pd) level of theory, a total of 62 vibrational states is found when J = 0. The complete vibrational levels, classical turning points, inertial rotation and centrifugal distortion constants for these vibrational states are also reported. The reasonable dissociation limit for this state is deduced using the calculated results at present. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] Convergence enhancement in the iterative solution of the second-order contracted Schrödinger equationINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2005D. R. Alcoba Abstract The iterative solution of the contracted Schrödinger equation is coupled with a second-order reduced density matrix purification procedure, which corrects its N- and S-representability defects, and with a regulating convergence device. An analysis of the effects of these new implementations is reported. The method is applied to the calculation of the potential energy curves of the BeH2 and Li2 molecules. The results compare very closely with those of the full configurations interaction. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source] Force-field parameters of the , and , around glycosidic bonds to oxygen and sulfur atomsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 16 2009Minoru Saito Abstract The , and , torsion angles around glycosidic bonds in a glycoside chain are the most important determinants of the conformation of a glycoside chain. We determined force-field parameters for , and , torsion angles around a glycosidic bond bridged by a sulfur atom, as well as a bond bridged by an oxygen atom as a preparation for the next study, i.e., molecular dynamics free energy calculations for protein-sugar and protein-inhibitor complexes. First, we extracted the , or , torsion energy component from a quantum mechanics (QM) total energy by subtracting all the molecular mechanics (MM) force-field components except for the , or , torsion angle. The , and , energy components extracted (hereafter called "the remaining energy components") were calculated for simple sugar models and plotted as functions of the , and , angles. The remaining energy component curves of , and , were well represented by the torsion force-field functions consisting of four and three cosine functions, respectively. To confirm the reliability of the force-field parameters and to confirm its compatibility with other force-fields, we calculated adiabatic potential curves as functions of , and , for the model glycosides by adopting the , and , force-field parameters obtained and by energetically optimizing other degrees of freedom. The MM potential energy curves obtained for , and , well represented the QM adiabatic curves and also these curves' differences with regard to the glycosidic oxygen and sulfur atoms. Our , and , force-fields of glycosidic oxygen gave MM potential energy curves that more closely represented the respective QM curves than did those of the recently developed GLYCAM force-field. © 2009 Wiley Periodicals, Inc., J Comput Chem, 2009 [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] Theoretical Study of the Reactions M++CH3F (M=Ge, As, Se, Sb)CHEMPHYSCHEM, Issue 9 2010Oscar Méndez Abstract CASSCF,MRMP2 calculations have been carried out to analyze the reactions of the methyl fluoride molecule with the atomic ions Ge+, As+, Se+ and Sb+. For these interactions, potential energy curves for the low-lying electronic states were calculated for different approaching modes of the fragments. Particularly, those channels leading to CH and CF oxidative addition products, H2FCMH+ and H3CMF+, respectively were explored, as well as the paths which evolve to the abstraction (MF++CH3) and the elimination (CH2M++HF) asymptotes. For the reaction Ge++CH3F the only favorable channel leads to fluorine abstraction by the ion. As+ and Sb+ can react with CH3F along pathways yielding stable addition products. However, a viable path joining the oxidative addition product H3CMF+ with the elimination asymptote CH2M++HF was found for the reaction of the fluorocarbon compound with As+. No favorable channels were detected for the interaction of fluoromethane with Se+. The results discussed herein allow rationalizing some of the experimental data found for these interactions through gas-phase mass spectrometry. [source] Ultrafast Relaxation Dynamics of the Excited States of 1-Amino- and 1-(N,N -Dimethylamino)-fluoren-9-onesCHEMPHYSCHEM, Issue 17 2009Mahendra Varne Abstract The dynamics of the excited states of 1-aminofluoren-9-one (1AF) and 1-(N,N -dimethylamino)-fluoren-9-one (1DMAF) are investigated by using steady-state absorption and fluorescence as well as subpicosecond time-resolved absorption spectroscopic techniques. Following photoexcitation of 1AF, which exists in the intramolecular hydrogen-bonded form in aprotic solvents, the excited-state intramolecular proton-transfer reaction is the only relaxation process observed in the excited singlet (S1) state. However, in protic solvents, the intramolecular hydrogen bond is disrupted in the excited state and an intermolecular hydrogen bond is formed with the solvent leading to reorganization of the hydrogen-bond network structure of the solvent. The latter takes place in the timescale of the process of solvation dynamics. In the case of 1DMAF, the main relaxation pathway for the locally excited singlet, S1(LE), or S1(ICT) state is the configurational relaxation, via nearly barrierless twisting of the dimethylamino group to form the twisted intramolecular charge-transfer, S1(TICT), state. A crossing between the excited-state and ground-state potential energy curves is responsible for the fast, radiationless deactivation and nonemissive character of the S1(TICT) state in polar solvents, both aprotic and protic. However, in viscous but strong hydrogen-bond-donating solvents, such as ethylene glycol and glycerol, crossing between the potential energy surfaces for the ground electronic state and the hydrogen-bonded complex formed between the S1(TICT) state and the solvent is possibly avoided and the hydrogen-bonded complex is weakly emissive. [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 Studies on Proton Transfer Reactions of 8-Hydroxyquinoline Monomers and DimersCHINESE JOURNAL OF CHEMISTRY, Issue 6 2006Ji-Yang Zhao Abstract Density functional theory (DFT) of quantum chemistry method was employed to investigate proton transfer reactions of 8-hydroxyquinoline (8-HQ) monomers and dimers. By studying the potential energy curves of the isomerization, the most possible reaction pathway was found. The total energy of 8-hydroxyquinoline was lower than that of quinolin-8(1H)-one, whereas the order was reversed in dimers. The findings explained the contrary experimental phenomena. The minimum reaction barrier of intramolecular proton transfer was 47.3 kJ/mol while that in dimer was only 25.7 kJ/mol. Hence it is obvious that proton transfer reactions of 8-HQ monomer have a considerable rate but it is easier to proceed for 8-HQ dimer than monomers. It implied that the hydrogen bond played an important role in depressing the activation energy of reaction. The mechanism of the tautomerization was discussed on the basis of theoretical results. [source] | ||||||||||