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Sample records for calculated potential energy

  1. New approach to calculating the potential energy of colliding nuclei

    SciTech Connect

    Kurmanov, R. S.; Kosenko, G. I.

    2014-12-15

    The differential method proposed by the present authors earlier for the reduction of volume integrals in calculating the potential energy of a compound nucleus is generalized to the case of two interacting nuclei. The Coulomb interaction energy is obtained for the cases of a sharp and a diffuse boundary of nuclei, while the nuclear interaction energy is found only for nuclei with a sharp boundary, the finiteness of the nuclear-force range being taken into account. The present method of calculations permits reducing the time it takes to compute the potential energy at least by two orders of magnitude.

  2. Nitroborazines as potential high energy materials: density functional theoretical calculations.

    PubMed

    Janning, Jay D; Ball, David W

    2010-05-01

    As part of a search for new high energy density materials, we used density functional theoretical calculations to determine the thermochemical properties of various nitro-substituted borazine molecules. Optimized geometries, vibrational frequencies and spectra, and enthalpies of formation and combustion were determined for nitroborazine, dinitroborazine, trinitroborazine, and methyltrinitroborazine with substituents on either the boron atoms or the nitrogen atoms of the parent borazine ring. Our results indicate that the specific enthalpy of combustion ranged from 4 to 11 kJ g(-1), with increasing substitution of nitro groups lowering the energy of combustion per unit mass.

  3. Potential Energy Calculations for Collinear Cluster Tripartition Fission Events

    NASA Astrophysics Data System (ADS)

    Unzhakova, A. V.; Pashkevich, V. V.; Pyatkov, Y. V.

    2014-09-01

    Strutinsky shell correction calculations were performed to describe the recent experimental results on collinear ternary fission. Collinear Cluster Tripartion fission events were studied experimentally in neutron induced fission of 235U, where the missing mass in the detected binary decay was suggested to characterize fission event as a collinear tripartition; and in spontaneous fission of 252Cf, where the direct detection of the three fission fragments has been used to confirm the existence of the Collinear Cluster Tripartition channel with a probability of 4.7×10-3 relative to the binary fission events.

  4. Hot-electron-mediated desorption rates calculated from excited-state potential energy surfaces

    NASA Astrophysics Data System (ADS)

    Olsen, Thomas; Gavnholt, Jeppe; Schiøtz, Jakob

    2009-01-01

    We present a model for desorption induced by (multiple) electronic transitions [DIET (DIMET)] based on potential energy surfaces calculated with the delta self-consistent field extension of density-functional theory. We calculate potential energy surfaces of CO and NO molecules adsorbed on various transition-metal surfaces and show that classical nuclear dynamics does not suffice for propagation in the excited state. We present a simple Hamiltonian describing the system with parameters obtained from the excited-state potential energy surface and show that this model can describe desorption dynamics in both the DIET and DIMET regimes and reproduce the power-law behavior observed experimentally. We observe that the internal stretch degree of freedom in the molecules is crucial for the energy transfer between the hot electrons and the molecule when the coupling to the surface is strong.

  5. Absolute Binding Free Energy Calculations Using Molecular Dynamics Simulations with Restraining Potentials

    PubMed Central

    Wang, Jiyao; Deng, Yuqing; Roux, Benoît

    2006-01-01

    The absolute (standard) binding free energy of eight FK506-related ligands to FKBP12 is calculated using free energy perturbation molecular dynamics (FEP/MD) simulations with explicit solvent. A number of features are implemented to improve the accuracy and enhance the convergence of the calculations. First, the absolute binding free energy is decomposed into sequential steps during which the ligand-surrounding interactions as well as various biasing potentials restraining the translation, orientation, and conformation of the ligand are turned “on” and “off.” Second, sampling of the ligand conformation is enforced by a restraining potential based on the root mean-square deviation relative to the bound state conformation. The effect of all the restraining potentials is rigorously unbiased, and it is shown explicitly that the final results are independent of all artificial restraints. Third, the repulsive and dispersive free energy contribution arising from the Lennard-Jones interactions of the ligand with its surrounding (protein and solvent) is calculated using the Weeks-Chandler-Andersen separation. This separation also improves convergence of the FEP/MD calculations. Fourth, to decrease the computational cost, only a small number of atoms in the vicinity of the binding site are simulated explicitly, while all the influence of the remaining atoms is incorporated implicitly using the generalized solvent boundary potential (GSBP) method. With GSBP, the size of the simulated FKBP12/ligand systems is significantly reduced, from ∼25,000 to 2500. The computations are very efficient and the statistical error is small (∼1 kcal/mol). The calculated binding free energies are generally in good agreement with available experimental data and previous calculations (within ∼2 kcal/mol). The present results indicate that a strategy based on FEP/MD simulations of a reduced GSBP atomic model sampled with conformational, translational, and orientational restraining

  6. Transformation of potential energy surfaces for estimating isotopic shifts in anharmonic vibrational frequency calculations

    SciTech Connect

    Meier, Patrick; Oschetzki, Dominik; Rauhut, Guntram; Berger, Robert

    2014-05-14

    A transformation of potential energy surfaces (PES) being represented by multi-mode expansions is introduced, which allows for the calculation of anharmonic vibrational spectra of any isotopologue from a single PES. This simplifies the analysis of infrared spectra due to significant CPU-time savings. An investigation of remaining deviations due to truncations and the so-called multi-level approximation is provided. The importance of vibrational-rotational couplings for small molecules is discussed in detail. In addition, an analysis is proposed, which provides information about the quality of the transformation prior to its execution. Benchmark calculations are provided for a set of small molecules.

  7. A refined quartic potential energy surface and large scale vibrational calculations for S0 thiophosgene.

    PubMed

    Rashev, Svetoslav; Moule, David C

    2015-04-01

    In this work we present a full 6D quartic potential energy surface (PES) for S0 thiophosgene in curvilinear symmetrized bond-angle coordinates. The PES was refined starting from an ab initio field derived from acc-pVTZ basis set with CCSD(T) corrections for electron correlation. In the present calculations we used our variational method that was recently tested on formaldehyde and some of its isotopomers, along with additional improvements. The lower experimentally known vibrational levels for 35Cl2CS were reproduced quite well in the calculations, which can be regarded as a test for the feasibility of the obtained quartic PES. PMID:25615683

  8. DFT calculations on nitrodiborane compounds as new potential high energy materials.

    PubMed

    Abdelmalik, John; Ball, David W

    2010-05-01

    We have used DFT methods to determine the structures and thermochemistry of several nitro-substituted diborane molecules in an attempt to rate their potential as high energy materials. The properties of nitrodiborane, three isomers of dinitrodiborane, trinitrodiborane, and tetranitrodiborane were calculated using the B3LYP density functional method. Our results indicate that the absolute enthalpy of combustion decreases with increasing nitro content, in contrast with other nitro-substituted systems that have been studied previously.

  9. Theoretical calculations and vibrational potential energy surface of 4-silaspiro(3,3)heptane

    SciTech Connect

    Ocola, Esther J.; Medders, Cross; Laane, Jaan; Meinander, Niklas

    2014-04-28

    Theoretical computations have been carried out on 4-silaspiro(3,3)heptane (SSH) in order to calculate its molecular structure and conformational energies. The molecule has two puckered four-membered rings with dihedral angles of 34.2° and a tilt angle of 9.4° between the two rings. Energy calculations were carried out for different conformations of SSH. These results allowed the generation of a two-dimensional ring-puckering potential energy surface (PES) of the form V = a(x{sub 1}{sup 4} + x{sub 2}{sup 4}) – b(x{sub 1}{sup 2} + x{sub 2}{sup 2}) + cx{sub 1}{sup 2}x{sub 2}{sup 2}, where x{sub 1} and x{sub 2} are the ring-puckering coordinates for the two rings. The presence of sufficiently high potential energy barriers prevents the molecule from undergoing pseudorotation. The quantum states, wave functions, and predicted spectra resulting from the PESs were calculated.

  10. Classical calculation of the equilibrium constants for true bound dimers using complete potential energy surface

    SciTech Connect

    Buryak, Ilya; Vigasin, Andrey A.

    2015-12-21

    The present paper aims at deriving classical expressions which permit calculation of the equilibrium constant for weakly interacting molecular pairs using a complete multidimensional potential energy surface. The latter is often available nowadays as a result of the more and more sophisticated and accurate ab initio calculations. The water dimer formation is considered as an example. It is shown that even in case of a rather strongly bound dimer the suggested expression permits obtaining quite reliable estimate for the equilibrium constant. The reliability of our obtained water dimer equilibrium constant is briefly discussed by comparison with the available data based on experimental observations, quantum calculations, and the use of RRHO approximation, provided the latter is restricted to formation of true bound states only.

  11. Classical calculation of the equilibrium constants for true bound dimers using complete potential energy surface

    NASA Astrophysics Data System (ADS)

    Buryak, Ilya; Vigasin, Andrey A.

    2015-12-01

    The present paper aims at deriving classical expressions which permit calculation of the equilibrium constant for weakly interacting molecular pairs using a complete multidimensional potential energy surface. The latter is often available nowadays as a result of the more and more sophisticated and accurate ab initio calculations. The water dimer formation is considered as an example. It is shown that even in case of a rather strongly bound dimer the suggested expression permits obtaining quite reliable estimate for the equilibrium constant. The reliability of our obtained water dimer equilibrium constant is briefly discussed by comparison with the available data based on experimental observations, quantum calculations, and the use of RRHO approximation, provided the latter is restricted to formation of true bound states only.

  12. Classical calculation of the equilibrium constants for true bound dimers using complete potential energy surface.

    PubMed

    Buryak, Ilya; Vigasin, Andrey A

    2015-12-21

    The present paper aims at deriving classical expressions which permit calculation of the equilibrium constant for weakly interacting molecular pairs using a complete multidimensional potential energy surface. The latter is often available nowadays as a result of the more and more sophisticated and accurate ab initio calculations. The water dimer formation is considered as an example. It is shown that even in case of a rather strongly bound dimer the suggested expression permits obtaining quite reliable estimate for the equilibrium constant. The reliability of our obtained water dimer equilibrium constant is briefly discussed by comparison with the available data based on experimental observations, quantum calculations, and the use of RRHO approximation, provided the latter is restricted to formation of true bound states only.

  13. Biasing Potential Replica Exchange Multi-Site λ-Dynamics for Efficient Free Energy Calculations

    PubMed Central

    Armacost, Kira A.; Goh, Garrett B.; Brooks, Charles L.

    2016-01-01

    Traditional free energy calculation methods are well known for their drawbacks in scalability and speed in converging results particularly for calculations with large perturbations. In the present work, we report on the development of biasing potential replica exchange multi-site λ-dynamics (BP-REX MSλD), which is a free energy method that is capable of performing simultaneous alchemical free energy transformations, including perturbations between flexible moieties. BP-REX MSλD and the original MSλD are applied to a series of symmetrical 2,5-benzoquinone derivatives covering a diverse chemical space and range of conformational flexibility. Improved λ-space sampling is observed for the BP-REX MSλD simulations, yielding a 2–5-fold increase in the number of transitions between substituents compared to traditional MSλD. We also demonstrate the efficacy of varying the value of c, the parameter that controls the ruggedness of the landscape mediating the sampling of λ-states, based on the flexibility of the fragment. Finally, we developed a protocol for maximizing the transition frequency between fragments. This protocol reduces the “kinetic barrier” for alchemically transforming fragments by grouping and ordering based on volume. These findings are applied to a challenging test set involving a series of geldanamycin-based inhibitors of heat shock protein 90 (Hsp90). Even though the perturbations span volume changes by as large as 60 Å3, the values for the free energy change achieve an average unsigned error (AUE) of 1.5 kcal/mol relative to experimental Kd measurements with a reasonable correlation (R = 0.56). Our results suggest that the BP-REX MSλD algorithm is a highly efficient and scalable free energy method, which when utilized will enable routine calculations on the order of hundreds of compounds using only a few simulations. PMID:26579773

  14. Temperature dependent effective potential method for accurate free energy calculations of solids

    NASA Astrophysics Data System (ADS)

    Hellman, Olle; Steneteg, Peter; Abrikosov, I. A.; Simak, S. I.

    2013-03-01

    We have developed a thorough and accurate method of determining anharmonic free energies, the temperature dependent effective potential technique (TDEP). It is based on ab initio molecular dynamics followed by a mapping onto a model Hamiltonian that describes the lattice dynamics. The formalism and the numerical aspects of the technique are described in detail. A number of practical examples are given, and results are presented, which confirm the usefulness of TDEP within ab initio and classical molecular dynamics frameworks. In particular, we examine from first principles the behavior of force constants upon the dynamical stabilization of the body centered phase of Zr, and show that they become more localized. We also calculate the phase diagram for 4He modeled with the Aziz potential and obtain results which are in favorable agreement both with respect to experiment and established techniques.

  15. Balanced Basis Sets in the Calculation of Potential Energy Curves for Diatomic Molecules.

    NASA Astrophysics Data System (ADS)

    Barclay, V. J.

    "Balanced" basis sets, which describe the internuclear region as well as the nuclear region, are examined in the context of an ab initio selection-extrapolation configuration -interaction method (MRD-CI). The sets are balanced by adding bond functions (BF's), which are s, p and d-type orbitals at the bond mid-point, to atomic-centred molecular basis sets, which have double and triple sets of valence -shell orbitals (DZ and TZ) and one or two sets of polarization functions (PF's). Potential energy curves and spectroscopic constants were calculated for the ground states of the hydrides H _2, OH, NaH, MgH, MH, SiH, PH, SH, HCl, and for the ionized species OH^+ and OH^{++}, and for the A^3Sigma_{u}, w^3Delta_{u} and B^3Pi_{g} excited states of N_2. The basis sets containing bond functions gave curves and constants superior to the DZP and (where calculated) TZPP results, and of quality similar to large basis set calculations in the literature. The single and double ionization potentials of OH, and the term energies of the N_2 excited states had error at the atomic asymptotes for all basis sets. The dissociation energies of the ground states of ten first-row diatomics (C_2, N_2, O_2, F_2, CN, CO, CF, NO, NF, and FO) were studied using balanced basis sets. A correlation was found to exist between the actual bond order of a species, and the number and kinds of orbitals which comprise the optimum BF. For MRD-CI diatomic calculations, the following BF's should be added to a DZP basis set (sp) (for a bond order of 1); 2(sp) (B. O. 1.5); (spd) (B. O. 2); 3(sp) (B. O. 2.5); 2(spd) (B. O. 3). The prescribed BF basis method was tested on the 26 second-row congeners Si _2, P_2, S _2, Cl_2, SiP, SiS, SiCl, PS, PCl, and ClS, and mixed-row congeners SiN, SiO, SiF, PO, PF, SF, SiC, PN, SO, ClF, CP, CS, CCl, NS, NCl, and ClO. An average error of 6% and a maximum error of 10% relative to known experimental D_{e }'s was found: compared to an average error of 18% for TZPP calculations

  16. Full dimension Rb2He ground triplet potential energy surface and quantum scattering calculations.

    PubMed

    Guillon, Grégoire; Viel, Alexandra; Launay, Jean-Michel

    2012-05-01

    We have developed a three-dimensional potential energy surface for the lowest triplet state of the Rb(2)He complex. A global analytic fit is provided as in the supplementary material [see supplementary material at http://dx.doi.org/10.1063/1.4709433 for the corresponding Fortran code]. This surface is used to perform quantum scattering calculations of (4)He and (3)He colliding with (87)Rb(2) in the partial wave J = 0 at low and ultralow energies. For the heavier helium isotope, the computed vibrational relaxation probabilities show a broad and strong shape resonance for a collisional energy of 0.15 K and a narrow Feshbach resonance at about 17 K for all initial Rb(2) vibrational states studied. The broad resonance corresponds to an efficient relaxation mechanism that does not occur when (3)He is the colliding partner. The Feshbach resonance observed at higher collisional energy is robust with respect to the isotopic substitution. However, its effect on the vibrational relaxation mechanism is faint for both isotopes. PMID:22583230

  17. Calculated ground state potential surface and excitation energies for the copper trimer

    NASA Technical Reports Server (NTRS)

    Walch, S. P.; Laskowski, B. C.

    1986-01-01

    In the context of their relevance to catalysis and to materials science problems, transition metals and transition metal (TM) compounds are currently of considerable interest, and studies have been conducted of the copper trimer, Cu3. The present investigation is concerned with a study of the ground state surface and several groups of excited states in order to improve the understanding of the spectroscopy of Cu3. Differences of the current study from previous investigations are related to an employment of larger basis sets and a more extensive electron correlation. This was done with the objective to obtain a more accurate definition of the ground state surface. Features of the bonding in the copper dimer are considered to obtain a basis for an understanding of the copper trimer. Attention is given to calculational details, the ground state surface, and calculated vertical excitation energies. The results of SCF/SDCI calculations are reported for portions of the ground surface, for two groups of excited states, and for the ionization potential of Cu3.

  18. An accurate potential energy curve for helium based on ab initio calculations

    NASA Astrophysics Data System (ADS)

    Janzen, A. R.; Aziz, R. A.

    1997-07-01

    Korona, Williams, Bukowski, Jeziorski, and Szalewicz [J. Chem. Phys. 106, 1 (1997)] constructed a completely ab initio potential for He2 by fitting their calculations using infinite order symmetry adapted perturbation theory at intermediate range, existing Green's function Monte Carlo calculations at short range and accurate dispersion coefficients at long range to a modified Tang-Toennies potential form. The potential with retardation added to the dipole-dipole dispersion is found to predict accurately a large set of microscopic and macroscopic experimental data. The potential with a significantly larger well depth than other recent potentials is judged to be the most accurate characterization of the helium interaction yet proposed.

  19. Accurate potential energy curve of the LiH{sup +} molecule calculated with explicitly correlated Gaussian functions

    SciTech Connect

    Tung, Wei-Cheng; Adamowicz, Ludwik

    2014-03-28

    Very accurate calculations of the ground-state potential energy curve (PEC) of the LiH{sup +} ion performed with all-electron explicitly correlated Gaussian functions with shifted centers are presented. The variational method is employed. The calculations involve optimization of nonlinear exponential parameters of the Gaussians performed with the aid of the analytical first derivatives of the energy determined with respect to the parameters. The diagonal adiabatic correction is also calculated for each PEC point. The PEC is then used to calculate the vibrational energies of the system. In that calculation, the non-adiabatic effects are accounted for by using an effective vibrational mass obtained by the minimization of the difference between the vibrational energies obtained from the calculations where the Born-Oppenheimer approximation was not assumed and the results of the present calculations.

  20. A terrain-dependent reference atmosphere determination method for available potential energy calculations

    NASA Technical Reports Server (NTRS)

    Koehler, T. L.

    1986-01-01

    An iterative technique that determines the reference atmosphere which incorporates the effects of uneven surface topography is presented. This method has been successfully applied in several available potential energy studies. An alternative method due to Taylor is also evaluated. While Taylor presented excellent continuous formulations of the available potential energy that include topography, his method for determining the reference atmosphere distributions failed to provide the accuracy needed to produce reliable available potential energy estimates. Since topography has a significant influence on the general circulation, it is important to employ techniques that incorporate its effects in the determination of available potential energy.

  1. Potential energy curves of Li+2 from all-electron EA-EOM-CCSD calculations

    NASA Astrophysics Data System (ADS)

    Musiał, Monika; Medrek, Magdalena; Kucharski, Stanisław A.

    2015-10-01

    The electron attachment (EA) equation-of-motion coupled-cluster theory provides description of the states obtained by the attachment of an electron to the reference system. If the reference is assumed to be a doubly ionised cation, then the EA results relate to the singly ionised ion. In the current work, the above scheme is applied to the calculations of the potential energy curves (PECs) of the Li+2 cation adopting the doubly ionised Li2 +2 structure as the reference system. The advantage of such computational strategy relies on the fact that the closed-shell Li2 +2 reference dissociates into closed-shell fragments (Li2 +2 ⇒ Li+ + Li+), hence the RHF (restricted Hartree-Fock) function can be used as the reference in the whole range of interatomic distances. This scheme offers the first principle method without any model or effective potential parameters for the description of the bond-breaking processes. In this study, the PECs and selected spectroscopic constants for 18 electronic states of the Li+2 ion were computed and compared with experimental and other theoretical results. †In honour of Professor Sourav Pal on the occasion of an anniversary in his private and scientific life.

  2. Accurate high level ab initio-based global potential energy surface and dynamics calculations for ground state of CH2(+).

    PubMed

    Li, Y Q; Zhang, P Y; Han, K L

    2015-03-28

    A global many-body expansion potential energy surface is reported for the electronic ground state of CH2 (+) by fitting high level ab initio energies calculated at the multireference configuration interaction level with the aug-cc-pV6Z basis set. The topographical features of the new global potential energy surface are examined in detail and found to be in good agreement with those calculated directly from the raw ab initio energies, as well as previous calculations available in the literature. In turn, in order to validate the potential energy surface, a test theoretical study of the reaction CH(+)(X(1)Σ(+))+H((2)S)→C(+)((2)P)+H2(X(1)Σg (+)) has been carried out with the method of time dependent wavepacket on the title potential energy surface. The total integral cross sections and the rate coefficients have been calculated; the results determined that the new potential energy surface can both be recommended for dynamics studies of any type and as building blocks for constructing the potential energy surfaces of larger C(+)/H containing systems.

  3. Conformational evaluation of DNA-carcinogen adducts using semi-empirical potential energy calculations

    SciTech Connect

    Verna, L.K.

    1992-01-01

    The covalent attachment of an aromatic amine to guanine C8 can produce a conformational change within the DNA molecule. This conformational change is likely to influence the altered DNA's biological capacity. The author used semi-empirical potential energy calculations to evaluate conformational patterns of DNA-aromatic amine adducts using the series: aniline, 4-aminobiphenyl, 2-aminofluorene and 1-aminopyrene. An exhaustive search was made of the conformational space for carcinogen modified two-base sequences. Information was incorporated into single stranded modified trimers. Modified strands were incorporated in duplex trimers. Nine-base modified duplexes were constructed and evaluated. This procedure produced distinctly different patterns for each aromatic amine investigated. It was apparent that the base sequence in which the carcinogen modification was found was crucial to the conformational change produced. At the dimer level, aniline allows both syn and anti guanine orientations at the carcinogen modification site. There were base-base and base-carcinogen stacked states, suggesting a flexible adduct easily able to assume many conformations. 4-Aminobiphenyl attachment resulted in low energy base-carcinogen stacked states, and a guanine torsion predominantly in a low syn orientation. The flexibility of this adduct was greatly reduced from that of the aniline adduct. 2-Aminofluorene adducts assumed more of a conformational mix. The major portion was base-base stacked with modified guanine anti, with a portion with base-carcinogen stacking and guanine syn or low syn. 1-Aminopyrene adducts were inflexible. The majority assumed a base-carcinogen stack with guanine syn. The conformational profiles of large modified pieces provided details of a unique low energy wedge conformation, in which aminofluorene, particularly, was able to fit into the minor groove with very little helix distortion.

  4. Full Dimensional Vibrational Calculations for Methane Using AN Accurate New AB Initio Based Potential Energy Surface

    NASA Astrophysics Data System (ADS)

    Majumder, Moumita; Dawes, Richard; Wang, Xiao-Gang; Carrington, Tucker; Li, Jun; Guo, Hua; Manzhos, Sergei

    2014-06-01

    New potential energy surfaces for methane were constructed, represented as analytic fits to about 100,000 individual high-level ab initio data. Explicitly-correlated multireference data (MRCI-F12(AE)/CVQZ-F12) were computed using Molpro [1] and fit using multiple strategies. Fits with small to negligible errors were obtained using adaptations of the permutation-invariant-polynomials (PIP) approach [2,3] based on neural-networks (PIP-NN) [4,5] and the interpolative moving least squares (IMLS) fitting method [6] (PIP-IMLS). The PESs were used in full-dimensional vibrational calculations with an exact kinetic energy operator by representing the Hamiltonian in a basis of products of contracted bend and stretch functions and using a symmetry adapted Lanczos method to obtain eigenvalues and eigenvectors. Very close agreement with experiment was produced from the purely ab initio PESs. References 1- H.-J. Werner, P. J. Knowles, G. Knizia, 2012.1 ed. 2012, MOLPRO, a package of ab initio programs. see http://www.molpro.net. 2- Z. Xie and J. M. Bowman, J. Chem. Theory Comput 6, 26, 2010. 3- B. J. Braams and J. M. Bowman, Int. Rev. Phys. Chem. 28, 577, 2009. 4- J. Li, B. Jiang and Hua Guo, J. Chem. Phys. 139, 204103 (2013). 5- S Manzhos, X Wang, R Dawes and T Carrington, JPC A 110, 5295 (2006). 6- R. Dawes, X-G Wang, A.W. Jasper and T. Carrington Jr., J. Chem. Phys. 133, 134304 (2010).

  5. Calculation of rotation-vibration energy levels of the ammonia molecule based on an ab initio potential energy surface

    NASA Astrophysics Data System (ADS)

    Polyansky, Oleg L.; Ovsyannikov, Roman I.; Kyuberis, Aleksandra A.; Lodi, Lorenzo; Tennyson, Jonathan; Yachmenev, Andrey; Yurchenko, Sergei N.; Zobov, Nikolai F.

    2016-09-01

    An ab initio potential energy surface (PES) for gas-phase ammonia NH3 has been computed using the methodology pioneered for water (Polyansky et al., 2013). Multireference configuration interaction calculations are performed at about 50 000 points using the aug-cc-pCVQZ and aug-cc-pCV5Z basis sets and basis set extrapolation. Relativistic and adiabatic surfaces are also computed. The points are fitted to a suitable analytical form, producing the most accurate ab initio PES for this molecule available. The rotation-vibration energy levels are computed using nuclear motion program TROVE in both linearised and curvilinear coordinates. Better convergence is obtained using curvilinear coordinates. Our results are used to assign the visible spectrum of 14NH3 recorded by Coy and Lehmann (1986). Rotation-vibration energy levels for the isotopologues NH2D, NHD2, ND3 and 15NH3 are also given. An ab initio value for the dissociation energy D0 of 14NH3 is also presented.

  6. Microscopic calculation of interacting boson model parameters by potential-energy surface mapping

    SciTech Connect

    Bentley, I.; Frauendorf, S.

    2011-06-15

    A coherent state technique is used to generate an interacting boson model (IBM) Hamiltonian energy surface which is adjusted to match a mean-field energy surface. This technique allows the calculation of IBM Hamiltonian parameters, prediction of properties of low-lying collective states, as well as the generation of probability distributions of various shapes in the ground state of transitional nuclei, the last two of which are of astrophysical interest. The results for krypton, molybdenum, palladium, cadmium, gadolinium, dysprosium, and erbium nuclei are compared with experiment.

  7. Dynamics study of the OH + NH3 hydrogen abstraction reaction using QCT calculations based on an analytical potential energy surface

    NASA Astrophysics Data System (ADS)

    Monge-Palacios, M.; Corchado, J. C.; Espinosa-Garcia, J.

    2013-06-01

    To understand the reactivity and mechanism of the OH + NH3 → H2O + NH2 gas-phase reaction, which evolves through wells in the entrance and exit channels, a detailed dynamics study was carried out using quasi-classical trajectory calculations. The calculations were performed on an analytical potential energy surface (PES) recently developed by our group, PES-2012 [Monge-Palacios et al. J. Chem. Phys. 138, 084305 (2013)], 10.1063/1.4792719. Most of the available energy appeared as H2O product vibrational energy (54%), reproducing the only experimental evidence, while only the 21% of this energy appeared as NH2 co-product vibrational energy. Both products appeared with cold and broad rotational distributions. The excitation function (constant collision energy in the range 1.0-14.0 kcal mol-1) increases smoothly with energy, contrasting with the only theoretical information (reduced-dimensional quantum scattering calculations based on a simplified PES), which presented a peak at low collision energies, related to quantized states. Analysis of the individual reactive trajectories showed that different mechanisms operate depending on the collision energy. Thus, while at high energies (Ecoll ≥ 6 kcal mol-1) all trajectories are direct, at low energies about 20%-30% of trajectories are indirect, i.e., with the mediation of a trapping complex, mainly in the product well. Finally, the effect of the zero-point energy constraint on the dynamics properties was analyzed.

  8. Dynamics study of the OH + NH3 hydrogen abstraction reaction using QCT calculations based on an analytical potential energy surface.

    PubMed

    Monge-Palacios, M; Corchado, J C; Espinosa-Garcia, J

    2013-06-01

    To understand the reactivity and mechanism of the OH + NH3 → H2O + NH2 gas-phase reaction, which evolves through wells in the entrance and exit channels, a detailed dynamics study was carried out using quasi-classical trajectory calculations. The calculations were performed on an analytical potential energy surface (PES) recently developed by our group, PES-2012 [Monge-Palacios et al. J. Chem. Phys. 138, 084305 (2013)]. Most of the available energy appeared as H2O product vibrational energy (54%), reproducing the only experimental evidence, while only the 21% of this energy appeared as NH2 co-product vibrational energy. Both products appeared with cold and broad rotational distributions. The excitation function (constant collision energy in the range 1.0-14.0 kcal mol(-1)) increases smoothly with energy, contrasting with the only theoretical information (reduced-dimensional quantum scattering calculations based on a simplified PES), which presented a peak at low collision energies, related to quantized states. Analysis of the individual reactive trajectories showed that different mechanisms operate depending on the collision energy. Thus, while at high energies (E(coll) ≥ 6 kcal mol(-1)) all trajectories are direct, at low energies about 20%-30% of trajectories are indirect, i.e., with the mediation of a trapping complex, mainly in the product well. Finally, the effect of the zero-point energy constraint on the dynamics properties was analyzed.

  9. Full-dimensional vibrational calculations for H5O2+ using an ab initio potential energy surface

    NASA Astrophysics Data System (ADS)

    McCoy, Anne B.; Huang, Xinchuan; Carter, Stuart; Landeweer, Marc Y.; Bowman, Joel M.

    2005-02-01

    We report quantum diffusion Monte Carlo (DMC) and variational calculations in full dimensionality for selected vibrational states of H5O2+ using a new ab initio potential energy surface [X. Huang, B. Braams, and J. M. Bowman, J. Chem. Phys. 122, 044308 (2005)]. The energy and properties of the zero-point state are focused on in the rigorous DMC calculations. OH-stretch fundamentals are also calculated using "fixed-node" DMC calculations and variationally using two versions of the code MULTIMODE. These results are compared with infrared multiphoton dissociation measurements of Yeh et al. [L. I. Yeh, M. Okumura, J. D. Myers, J. M. Price, and Y. T. Lee, J. Chem. Phys. 91, 7319 (1989)]. Some preliminary results for the energies of several modes of the shared hydrogen are also reported.

  10. Ab Initio Potential Energy Surfaces and the Calculation of Accurate Vibrational Frequencies

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Dateo, Christopher E.; Martin, Jan M. L.; Taylor, Peter R.; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    Due to advances in quantum mechanical methods over the last few years, it is now possible to determine ab initio potential energy surfaces in which fundamental vibrational frequencies are accurate to within plus or minus 8 cm(exp -1) on average, and molecular bond distances are accurate to within plus or minus 0.001-0.003 Angstroms, depending on the nature of the bond. That is, the potential energy surfaces have not been scaled or empirically adjusted in any way, showing that theoretical methods have progressed to the point of being useful in analyzing spectra that are not from a tightly controlled laboratory environment, such as vibrational spectra from the interstellar medium. Some recent examples demonstrating this accuracy will be presented and discussed. These include the HNO, CH4, C2H4, and ClCN molecules. The HNO molecule is interesting due to the very large H-N anharmonicity, while ClCN has a very large Fermi resonance. The ab initio studies for the CH4 and C2H4 molecules present the first accurate full quartic force fields of any kind (i.e., whether theoretical or empirical) for a five-atom and six-atom system, respectively.

  11. Communication: MULTIMODE calculations of low-lying vibrational states of NO3 using an adiabatic potential energy surface

    NASA Astrophysics Data System (ADS)

    Homayoon, Zahra; Bowman, Joel M.

    2014-10-01

    A semi-global, permutationally invariant potential energy surface for NO3 is constructed from a subset of roughly 5000 Multi-State CASPT2 calculations (MS-CAS(17e,13o)PT2/aug-cc-pVTZ) reported by Morokuma and co-workers [H. Xiao, S. Maeda, and K. Morokuma, J. Chem. Theory Comput. 8, 2600 (2012)]. The PES, with empirical adjustments to modify the energies of two fundamentals and a hot-band transition, is used in full-dimensional vibrational self-consistent field/virtual state configuration interaction calculations using the code MULTIMODE. Vibrational energies and assignments are given for the fundamentals and low-lying combination states, including two that have been the focus of some controversy. Energies of a number of overtone and combinations are shown to be in good agreement with experiment and previous calculations using a model vibronic Hamiltonian [C. S. Simmons, T. Ichino, and J. F. Stanton, J. Phys. Chem. Lett. 3, 1946 (2012)]. Notably, the fundamental v3 is calculated to be at 1099 cm-1 in accord with the prediction from the vibronic analysis, although roughly 30 cm-1 higher. The state at 1493 cm-1 is assigned as v3 + v4, which is also in agreement with the vibronic analysis and some experiments. Vibrational energies for 15NO3 are also presented and these are also in good agreement with experiment.

  12. Progress Towards the Accurate Calculation of Anharmonic Vibrational States of Fluxional Molecules and Clusters Without a Potential Energy Surface

    NASA Astrophysics Data System (ADS)

    Petit, Andrew S.; McCoy, Anne B.

    2011-06-01

    The accurate calculation of anharmonic vibrational states of highly fluxional systems is complicated by the need to first obtain the full-dimensional potential energy surface(PES). Although commonly exploited as a way around this problem, grid-based methodologies scale exponentially with system size while reduced dimensional approaches are highly system dependent, both in terms of the details of their application and in terms of their suitability. Moreover, the achievement of converged variational calculations of highly anharmonic systems is complicated by the necessity of using a very large basis and hence the construction and diagonalization of enormous Hamiltonian matrices. We report here our recent efforts to develop an algorithm capable of accurately calculating anharmonic vibrational energies, even for very floppy systems, without first obtaining a PES and using only a handful of basis functions per degree of freedom. More specifically, the potential energy and G-matrix elements are calculated on a set of points obtained from a Monte Carlo sampling of the most important regions of configuration space, allowing for a significant reduction in the number of required sampling points. The Hamiltonian matrix is then constructed using an evolving basis which, with each iteration, captures the effect of building H from an ever-expanding basis despite the fact that the actual dimensionality of H is fixed throughout the calculation. This latter property of the algorithm also greatly reduces the size of basis needed for the calculation relative to more traditional variational approaches. The results obtained from the application of our method to several test systems, including ion water complexes, will be reported along with its observed convergence properties.

  13. Ab initio projected-unrestricted Hartree-Fock calculation of some potential energy curves for carbonyl fluoride

    NASA Technical Reports Server (NTRS)

    Brewer, D. A.; Schug, J. C.; Phillips, D. H.

    1980-01-01

    Some potential energy curves for CF2O were calculated using projected-unrestricted Hartree-Fock (PUHF) theory. The calculations employed a contracted (4s 3p) Gaussian-type atomic orbital basis set. Bound states were found for the X-tilde 1A1 and 1,3A2 states while the 1,3B1 and 1,3B2 states were repulsive in the valence representation. The merits of the PUHF treatment for excited states are discussed. The results are discussed in terms of available experimental information and previous calculations with particular emphasis on the question of the photolysis channels open in the solar spectral region.

  14. Calculate and Plot Complex Potential

    1998-05-05

    SOLUPLOT is a program designed to calculate and plot complex potential, pH diagrams and log oxygen activity, pH diagrams for aqueous chemical syatems, considering speciation of ligands, from free energy and thermodynamic activity data. These diagrams, commonly referred to as Eh-pH and ao2-pH diagrams, respectively, define areas of predominance in Eh-pH diagrams or ao2-pH space for chemical species of a chemical system at equilibrium. Over an area of predominance, one predominant species is at greatermore » activity than the other species of the system considered. The diagram axes, pH (a measure of hydrogen ion activity) and either Eh or log ao2 (measures of a tendency toward either oxidation or reduction) , are paremeters commonly applied in describing the chemistry of aqueous systems.« less

  15. An improved potential energy surface and multi-temperature quasiclassical trajectory calculations of N2 + N2 dissociation reactions.

    PubMed

    Bender, Jason D; Valentini, Paolo; Nompelis, Ioannis; Paukku, Yuliya; Varga, Zoltan; Truhlar, Donald G; Schwartzentruber, Thomas; Candler, Graham V

    2015-08-01

    Accurate modeling of high-temperature hypersonic flows in the atmosphere requires consideration of collision-induced dissociation of molecular species and energy transfer between the translational and internal modes of the gas molecules. Here, we describe a study of the N2 + N2⟶N2 + 2N and N2 + N2⟶4N nitrogen dissociation reactions using the quasiclassical trajectory (QCT) method. The simulations used a new potential energy surface for the N4 system; the surface is an improved version of one that was presented previously. In the QCT calculations, initial conditions were determined based on a two-temperature model that approximately separates the translational-rotational temperature from the vibrational temperature of the N2 diatoms. Five values from 8000 K to 30,000 K were considered for each of the two temperatures. Over 2.4 × 10(9) trajectories were calculated. We present results for ensemble-averaged dissociation rate constants as functions of the translational-rotational temperature T and the vibrational temperature T(v). The rate constant depends more strongly on T when T(v) is low, and it depends more strongly on T(v) when T is low. Quasibound reactant states contribute significantly to the rate constants, as do exchange processes at higher temperatures. We discuss two sets of runs in detail: an equilibrium test set in which T = T(v) and a nonequilibrium test set in which T(v) < T. In the equilibrium test set, high-v and moderately-low-j molecules contribute most significantly to the overall dissociation rate, and this state specificity becomes stronger as the temperature decreases. Dissociating trajectories tend to result in a major loss of vibrational energy and a minor loss of rotational energy. In the nonequilibrium test set, as T(v) decreases while T is fixed, higher-j molecules contribute more significantly to the dissociation rate, dissociating trajectories tend to result in a greater rotational energy loss, and the dissociation probability

  16. Potential of mean force calculation of the free energy of adsorption of Type I winter flounder antifreeze protein on ice

    NASA Astrophysics Data System (ADS)

    Battle, Keith; Alan Salter, E.; Wesley Edmunds, R.; Wierzbicki, Andrzej

    2010-04-01

    Antifreeze proteins (AFPs) are a unique class of proteins that inhibit ice growth without changing the melting point of ice. In this work, we study the detailed molecular mechanism of interactions between the hydrophobic side of the winter flounder (WF) AFP and two mutants, AAAA and SSSS, in which threonine residues are substituted by serines and alanines, respectively. Umbrella sampling molecular dynamics simulations of the separation of the proteins from the (2 0 1) surface in an explicit water box is carried out to calculate the potential of mean force free energies of adsorption using AMBER10i. We estimate wild-type WF's free energy of adsorption to ice to be about -12.0 kcal/mol. Gas-phase pseudopotential plane-wave calculations of methane adsorption onto select surfaces of ice are also carried out under periodic boundary conditions to address the possible enthalpic role of WF's methyl groups in binding. The contributions of hydrophobic residues to the free energy of adsorption are discussed.

  17. Quantum Chemical Calculations of the Cl- + CH3I → CH3Cl + I- Potential Energy Surface

    SciTech Connect

    Zhang, Jiaxu; Lourderaj, Upakarasamy; Addepalli, Srirangam V.; De Jong, Wibe A.; Hase, William L.

    2008-12-30

    Electronic structure theory calculations, using MP2 theory and the DFT functionals OPBE, OLYP, HCTH407, BhandH, and B97-1, were performed to characterize the structures, vibrational frequencies, and energies for stationary points on the Cl- + CH3I → ClCH3 + I- potential energy surface. The aug-cc-pVDZ and aug-cc-pVTZ basis sets, with an effective core potential (ECP) for iodine, were employed. Single-point CCSD(T) calculations were performed to obtain the complete basis set (CBS) limit for the reaction energies. DFT was found to give significantly longer halide ion/carbon atom bond lengths for the ion-dipole complexes and central barrier transition state, than MP2. BhandH, with either the aug-cc-pVDZ and aug-cc-pVTZ basis sets, gives good agreement with the experimental structures for both CH3I and CH3Cl. The frequencies of CH3I and CH3Cl, obtained with the different level of theory and basis sets, are in excellent agreement with experiment. The major difference between the MP2 and DFT frequencies is for the imaginary frequency of the central barrier. Using the aug-cc-pVTZ basis the MP2 value for this frequency ranges from 1.26 - 1.59 times larger than those for the DFT functional. Thus, the MP2 and DFT theories have different PES shapes in the vicinity of the [Cl--CH3--I]- central barrier. The CCSD(T)/CBS energies are in good agreement with experiments for the complexation energies and reaction exothermicity, with a small 1 kcal/mol difference for the latter. The CCSD(T)/CBS central barrier height is lower than values deduced by using statistical theoretical models to fit the Cl- + CH3I → ClCH3 + I- experimental rate constant, which is consistent with the expected non-statistical dynamics for the reaction. The BhandH energies are in overall best agreement with the CCSD(T) values, with a largest difference of only 0.7 kcal/mol.

  18. Probing calculated O2+ potential-energy curves with an XUV-IR pump-probe experiment

    NASA Astrophysics Data System (ADS)

    Cörlin, Philipp; Fischer, Andreas; Schönwald, Michael; Sperl, Alexander; Mizuno, Tomoya; Thumm, Uwe; Pfeifer, Thomas; Moshammer, Robert

    2015-04-01

    We study dissociative photoionization of molecular oxygen in a kinematically complete XUV-IR pump-probe experiment. Detecting charged fragments and photoelectrons in coincidence using a reaction microscope, we observe a pump-probe delay-dependent yield of very low energetic O+ ions which oscillates with a period of 40 fs . This feature is caused by a time-dependent vibrational wave packet in the potential of the binding O2+(a Π4u) state, which is probed by resonant absorption of a single infrared photon to the weakly repulsive O2+(f Π4g) state. By quantitative comparison of the experimental kinetic-energy-release (KER) and quantum-beat (QB) spectra with the results of a coupled-channel simulation, we are able to discriminate between the calculated adiabatic O2+ potential-energy curves (PECs) of Marian et al. [Marian, Marian, Peyerimhoff, Hess, Buenker, and Seger, Mol. Phys. 46, 779 (1982), 10.1080/00268978200101591] and Magrakvelidze et al. [Magrakvelidze, Aikens, and Thumm, Phys. Rev. A 86, 023402 (2012), 10.1103/PhysRevA.86.023402]. In general, we find a good agreement between experimental and simulated KER and QB spectra. However, we could not reproduce all features of the experimental data with these PECs. In contrast, adjusting a Morse potential to the experimental data, most features of the experimental spectra are well reproduced by our simulation. By comparing this Morse potential to theoretically predicted PECs, we demonstrate the sensitivity of our experimental method to small changes in the shape of the binding potential.

  19. Two-electron R-matrix approach to calculations of potential-energy curves of long-range Rydberg molecules

    NASA Astrophysics Data System (ADS)

    Tarana, Michal; Čurík, Roman

    2016-05-01

    We introduce a computational method developed for study of long-range molecular Rydberg states of such systems that can be approximated by two electrons in a model potential of the atomic cores. The method is based on a two-electron R-matrix approach inside a sphere centered on one of the atoms. The wave function is then connected to a Coulomb region outside the sphere via a multichannel version of the Coulomb Green's function. This approach is applied to a study of Rydberg states of Rb2 for internuclear separations R from 40 to 320 bohrs and energies corresponding to n from 7 to 30. We report bound states associated with the low-lying 3Po resonance and with the virtual state of the rubidium atom that turn into ion-pair-like bound states in the Coulomb potential of the atomic Rydberg core. The results are compared with previous calculations based on single-electron models employing a zero-range contact-potential and short-range modele potential. Czech Science Foundation (Project No. P208/14-15989P).

  20. Calculations of H2O microwave line broadening in collisions with He atoms - Sensitivity to potential energy surfaces

    NASA Technical Reports Server (NTRS)

    Green, Sheldon; Defrees, D. J.; Mclean, A. D.

    1991-01-01

    Theoretical computations of broadening parameters are reported for three microwave lines of H2O in a bath of He atoms. The potential-energy surfaces employed are corrected for basis-set superposition error, and their reliability is checked by repeating the calculations with a different basis set for orbital expansion. The results are presented in extensive tables and discussed in detail. The corrections applied are shown to have a significant impact on the accuracy of the room-temperature broadenings determined: 8.9 sq A for the 22.2-GHz line, 11.8 sq A for the 183,3-GHz line, and 10.0 sq A for the 380.2-GHz line, in good agreement with published experimental data. The importance of collisional broadening for the atmospheric transmission of radiation and for remote-sensing applications is indicated.

  1. MULTIMODE quantum calculations of vibrational energies and IR spectrum of the NO{sup +}(H{sub 2}O) cluster using accurate potential energy and dipole moment surfaces

    SciTech Connect

    Homayoon, Zahra

    2014-09-28

    A new, full (nine)-dimensional potential energy surface and dipole moment surface to describe the NO{sup +}(H{sub 2}O) cluster is reported. The PES is based on fitting of roughly 32 000 CCSD(T)-F12/aug-cc-pVTZ electronic energies. The surface is a linear least-squares fit using a permutationally invariant basis with Morse-type variables. The PES is used in a Diffusion Monte Carlo study of the zero-point energy and wavefunction of the NO{sup +}(H{sub 2}O) and NO{sup +}(D{sub 2}O) complexes. Using the calculated ZPE the dissociation energies of the clusters are reported. Vibrational configuration interaction calculations of NO{sup +}(H{sub 2}O) and NO{sup +}(D{sub 2}O) using the MULTIMODE program are performed. The fundamental, a number of overtone, and combination states of the clusters are reported. The IR spectrum of the NO{sup +}(H{sub 2}O) cluster is calculated using 4, 5, 7, and 8 modes VSCF/CI calculations. The anharmonic, coupled vibrational calculations, and IR spectrum show very good agreement with experiment. Mode coupling of the water “antisymmetric” stretching mode with the low-frequency intermolecular modes results in intensity borrowing.

  2. Gas-phase reaction between calcium monocation and fluoromethane: Analysis of the potential energy hypersurface and kinetics calculations

    SciTech Connect

    Varela-Alvarez, Adrian; Sordo, Jose A.; Rayon, V. M.; Redondo, P.; Barrientos, C.

    2009-10-14

    The gas-phase reaction between calcium monocation and fluoromethane: Ca{sup +}+CH{sub 3}F{yields}CaF{sup +}+CH{sub 3} was theoretically analyzed. The potential energy hypersurface was explored by using density functional theory methodology with different functionals and Pople's, Dunning's, Ahlrichs', and Stuttgart-Dresden basis sets. Kinetics calculations (energy and total angular momentum resolved microcanonical variational/conventional theory) were accomplished. The theoretically predicted range for the global kinetic rate constant values at 295 K (7.2x10{sup -11}-5.9x10{sup -10} cm{sup 3} molecule{sup -1} s{sup -1}) agrees reasonably well with the experimental value at the same temperature [(2.6{+-}0.8)x10{sup -10} cm{sup 3} molecule{sup -1} s{sup -1}]. Explicit consideration of a two transition state model, where the formation of a weakly bounded prereactive complex is preceded by an outer transition state (entrance channel) and followed by an inner transition state connecting with a second intermediate that finally leads to products, is mandatory. Experimental observations on the correlation, or lack of correlation, between reaction rate constants and second ionization energies of the metal might well be rationalized in terms of this two transition state model.

  3. Collisional excitation of CH(X²Π) by He: new ab initio potential energy surfaces and scattering calculations.

    PubMed

    Marinakis, Sarantos; Dean, Indigo Lily; Kłos, Jacek; Lique, François

    2015-09-01

    We present a new set of potential energy surfaces (PESs) for the CH(X(2)Π)-He van der Waals system. Ab initio calculations of the CH-He PES were carried out using the open-shell single- and double-excitation coupled cluster approach with non-iterative perturbational treatment of triple excitations [RCCSD(T)]. The augmented correlation-consistent polarized valence quadruple-zeta (aug-cc-pVQZ) basis set was employed augmented by mid-bond functions. Integral cross sections for the rotational excitation in CH-He collisions were calculated using the new PES and compared with available experimental results. The newly constructed PES reproduces the available experimental results for CH(X(2)Π, v = 0)-He collisions better than any previously available PES. Differential cross sections (DCS) are presented for the first time for this system and discussed within the context of rotational rainbows. Finally, our work provides the first rate thermal coefficients for this system that are crucially needed for astrochemical modelling and future anticipated experiments in CH(X(2)Π)-He collisions. PMID:26220835

  4. Accurate high level ab initio-based global potential energy surface and dynamics calculations for ground state of CH{sub 2}{sup +}

    SciTech Connect

    Li, Y. Q.; Zhang, P. Y.; Han, K. L.

    2015-03-28

    A global many-body expansion potential energy surface is reported for the electronic ground state of CH{sub 2}{sup +} by fitting high level ab initio energies calculated at the multireference configuration interaction level with the aug-cc-pV6Z basis set. The topographical features of the new global potential energy surface are examined in detail and found to be in good agreement with those calculated directly from the raw ab initio energies, as well as previous calculations available in the literature. In turn, in order to validate the potential energy surface, a test theoretical study of the reaction CH{sup +}(X{sup 1}Σ{sup +})+H({sup 2}S)→C{sup +}({sup 2}P)+H{sub 2}(X{sup 1}Σ{sub g}{sup +}) has been carried out with the method of time dependent wavepacket on the title potential energy surface. The total integral cross sections and the rate coefficients have been calculated; the results determined that the new potential energy surface can both be recommended for dynamics studies of any type and as building blocks for constructing the potential energy surfaces of larger C{sup +}/H containing systems.

  5. Calculation of Rotation-Vibration Energy Levels of the Water Molecule with Near-Experimental Accuracy Based on an ab Initio Potential Energy Surface

    NASA Astrophysics Data System (ADS)

    Polyansky, Oleg L.; Ovsyannikov, Roman I.; Kyuberis, Aleksandra A.; Lodi, Lorenzo; Tennyson, Jonathan; Zobov, Nikolai F.

    2013-10-01

    A recently computed, high-accuracy ab initio Born-Oppenheimer (BO) potential energy surface (PES) for the water molecule is combined with relativistic, adiabatic, quantum electrodynamics, and, crucially, nonadiabatic corrections. Calculations of ro-vibrational levels are presented for several water isotopologues and shown to have unprecedented accuracy. A purely ab initio calculation reproduces some 200 known band origins associated with seven isotopologues of water with a standard deviation (σ) of about 0.35 cm-1. Introducing three semiempirical scaling parameters, two affecting the BO PES and one controlling nonadiabatic effects, reduces σ below 0.1 cm-1. Introducing one further rotational nonadiabatic parameter gives σ better than 0.1 cm-1 for all observed ro-vibrational energy levels up to J = 25. We conjecture that the energy levels of closed-shell molecules with roughly the same number of electrons as water, such as NH3, CH4, and H3O+, could be calculated to this accuracy using an analogous procedure. This means that near-ab initio calculations are capable of predicting transition frequencies with an accuracy only about a factor of 5 worse than high resolution experiments.

  6. A potential energy surface for the process H2 + H2O yielding H + H + H2O - Ab initio calculations and analytical representation

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Walch, Stephen P.; Taylor, Peter R.

    1991-01-01

    Extensive ab initio calculations on the ground state potential energy surface of H2 + H2O were performed using a large contracted Gaussian basis set and a high level of correlation treatment. An analytical representation of the potential energy surface was then obtained which reproduces the calculated energies with an overall root-mean-square error of only 0.64 mEh. The analytic representation explicitly includes all nine internal degrees of freedom and is also well behaved as the H2 dissociates; it thus can be used to study collision-induced dissociation or recombination of H2. The strategy used to minimize the number of energy calculations is discussed, as well as other advantages of the present method for determining the analytical representation.

  7. Vibrational spectra, theoretical calculations, and two-dimensional potential energy surface for the ring-puckering vibrations of 2,4,7-trioxa[3.3.0]octane.

    PubMed

    Chun, Hye Jin; Meinander, Niklas; Villarreal, John R; Laane, Jaan

    2015-01-15

    2,4,7-Trioxa[3.3.0]octane (247TOO) is an unusual bicyclic molecule which can exist in four different conformational forms which are determined by the directions of the two ring- puckering motions. The vibrational assignments of 247TOO have been made based on its infrared and Raman spectra and theoretical density functional theory (DFT) calculations. The two ring-puckering motions (in-phase and out-of-phase) were observed in the Raman spectra of the liquid at 249 and 205 cm(-1) and these values correspond well to the DFT values of 247 and 198 cm(-1). Ab initio calculations were utilized to calculate the structures and conformational energies for the four energy minima and the barriers to interconversion and the data was utilized to generate a two-dimensional potential energy surface (PES) for the two ring-puckering motions. The resulting quantum state energies for this PES were then calculated in order to better understand the patterns that are produced when the PES has four energy minima at different energy values. The wave functions corresponding to the different quantum states were also calculated. The NMR spectrum of 247TOO showed the presence of the two lowest energy conformations, consistent with the results of the ab initio calculations. PMID:25514365

  8. Vibrational spectra, theoretical calculations, and two-dimensional potential energy surface for the ring-puckering vibrations of 2,4,7-trioxa[3.3.0]octane.

    PubMed

    Chun, Hye Jin; Meinander, Niklas; Villarreal, John R; Laane, Jaan

    2015-01-15

    2,4,7-Trioxa[3.3.0]octane (247TOO) is an unusual bicyclic molecule which can exist in four different conformational forms which are determined by the directions of the two ring- puckering motions. The vibrational assignments of 247TOO have been made based on its infrared and Raman spectra and theoretical density functional theory (DFT) calculations. The two ring-puckering motions (in-phase and out-of-phase) were observed in the Raman spectra of the liquid at 249 and 205 cm(-1) and these values correspond well to the DFT values of 247 and 198 cm(-1). Ab initio calculations were utilized to calculate the structures and conformational energies for the four energy minima and the barriers to interconversion and the data was utilized to generate a two-dimensional potential energy surface (PES) for the two ring-puckering motions. The resulting quantum state energies for this PES were then calculated in order to better understand the patterns that are produced when the PES has four energy minima at different energy values. The wave functions corresponding to the different quantum states were also calculated. The NMR spectrum of 247TOO showed the presence of the two lowest energy conformations, consistent with the results of the ab initio calculations.

  9. Low temperature rate constants for the N + CN → N2 + C reaction: two-dimensional quantum capture calculations on an accurate potential energy surface.

    PubMed

    Ma, Jianyi; Guo, Hua; Dawes, Richard

    2012-09-21

    The title reaction is thought to be responsible for the production of molecular nitrogen in interstellar clouds. In this work, we report quantum capture calculations on a new two-dimensional potential energy surface determined by interpolating high-level ab initio data. The low-temperature rate constant calculated using a capture model is quite large and has a positive temperature dependence, in agreement with a recent experiment. The origin of the aforementioned behaviors of the rate constant is analyzed.

  10. Benchmark Quantum Mechanical Calculations of Vibrationally Resolved Cross Sections and Rate Constants on ab Initio Potential Energy Surfaces for the F + HD Reaction: Comparisons with Experiments.

    PubMed

    De Fazio, Dario; Cavalli, Simonetta; Aquilanti, Vincenzo

    2016-07-14

    Quantum scattering calculations within the time-independent approach in an extended interval of energies were performed for the title reaction on four ab initio potential energy surfaces. The calculated integral cross sections, vibrational branching ratios, and rate constants are compared with scattering experiments as well as with chemical kinetics rate data available for this system for both the HF and DF channels. The calculations on the CSZ (J. Chem. Phys. 2015, 142, 024303) and LWAL (J. Chem. Phys. 2007, 127, 174302) surfaces are in close agreement between them and reproduce satisfactorily the experimental measurements. The agreement with the experiments is improved with respect to calculations on the earlier SW (J. Chem. Phys. 1996, 104, 6515) and FXZ (J. Chem. Phys. 2008, 129, 011103) surfaces. The results presented here witness the remarkable progress made by quantum chemistry calculations in describing the interatomic interactions governing the dynamics and kinetics of this reaction. They also suggest that comparison with translationally and rotationally averaged experimental observables is not sufficient to assess the relative accuracy of highly accurate potential energy surfaces. The dynamics and kinetics calculations show that temperatures lower than 50 K or molecular beam energy spread below 1 meV must be reached to discriminate the accuracy of the LWAL and the CSZ surfaces.

  11. CALCULATED MOLECULAR STRUCTURES AND POTENTIAL ENERGY FUNCTIONS OF PAHS WITH METHYL CROWDING IN THE BAY REGION AND THEIR METABOLITES: COMPARISON TO EXPERIMENTAL STRUCTURES

    EPA Science Inventory

    Abstract Title: Calculated molecular structures and potential energy functions of P AHs with methyl crowding in the bay region and their metabolites: Comparison to experimental structures.

    Abstract:
    PAHs with methyl group substitution near a bay region represent a cl...

  12. CALCULATED MOLECULAR STRUCTURES AND POTENTIAL ENERGY FUNCTIONS OF PAHS WITH METHYL CROWDING IN THE BAY REGION AND THEIR METABOLITES: COMPARISON TO EXPERIMENTAL STRUCTURES

    EPA Science Inventory

    Calculated molecular structures and potential energy functions ofP AHs with methyl crowding in the bay region and their metabolites: Comparison to experimental structures

    PAHs with methyl group substitution near a bay region represent a class of chemicals associated with ...

  13. Model potential calculations of lithium transitions.

    NASA Technical Reports Server (NTRS)

    Caves, T. C.; Dalgarno, A.

    1972-01-01

    Semi-empirical potentials are constructed that have eigenvalues close in magnitude to the binding energies of the valence electron in lithium. The potentials include the long range polarization force between the electron and the core. The corresponding eigenfunctions are used to calculate dynamic polarizabilities, discrete oscillator strengths, photoionization cross sections and radiative recombination coefficients. A consistent application of the theory imposes a modification on the transition operator, but its effects are small for lithium. The method presented can be regarded as a numerical generalization of the widely used Coulomb approximation.

  14. Fit Point-Wise AB Initio Calculation Potential Energies to a Multi-Dimension Long-Range Model

    NASA Astrophysics Data System (ADS)

    Zhai, Yu; Li, Hui; Le Roy, Robert J.

    2016-06-01

    A potential energy surface (PES) is a fundamental tool and source of understanding for theoretical spectroscopy and for dynamical simulations. Making correct assignments for high-resolution rovibrational spectra of floppy polyatomic and van der Waals molecules often relies heavily on predictions generated from a high quality ab initio potential energy surface. Moreover, having an effective analytic model to represent such surfaces can be as important as the ab initio results themselves. For the one-dimensional potentials of diatomic molecules, the most successful such model to date is arguably the ``Morse/Long-Range'' (MLR) function developed by R. J. Le Roy and coworkers. It is very flexible, is everywhere differentiable to all orders. It incorporates correct predicted long-range behaviour, extrapolates sensibly at both large and small distances, and two of its defining parameters are always the physically meaningful well depth {D}_e and equilibrium distance r_e. Extensions of this model, called the Multi-Dimension Morse/Long-Range (MD-MLR) function, linear molecule-linear molecule systems and atom-non-linear molecule system. have been applied successfully to atom-plus-linear molecule, linear molecule-linear molecule and atom-non-linear molecule systems. However, there are several technical challenges faced in modelling the interactions of general molecule-molecule systems, such as the absence of radial minima for some relative alignments, difficulties in fitting short-range potential energies, and challenges in determining relative-orientation dependent long-range coefficients. This talk will illustrate some of these challenges and describe our ongoing work in addressing them. Mol. Phys. 105, 663 (2007); J. Chem. Phys. 131, 204309 (2009); Mol. Phys. 109, 435 (2011). Phys. Chem. Chem. Phys. 10, 4128 (2008); J. Chem. Phys. 130, 144305 (2009) J. Chem. Phys. 132, 214309 (2010) J. Chem. Phys. 140, 214309 (2010)

  15. Charging free energy calculations using the Generalized Solvent Boundary Potential (GSBP) and periodic boundary condition: a comparative analysis using ion solvation and oxidation free energy in proteins.

    PubMed

    Lu, Xiya; Cui, Qiang

    2013-02-21

    Free energy simulations using a finite sphere boundary condition rather than a periodic boundary condition (PBC) are attractive in the study of very large biomolecular systems. To understand the quantitative impact of various approximations in such simulations, we compare charging free energies in both solution and protein systems calculated in a linear response framework with the Generalized Solvent Boundary Potential (GSBP) and PBC simulations. For simple ions in solution, we find good agreements between GSBP and PBC charging free energies, once the relevant correction terms are taken into consideration. For PBC simulations with the particle-mesh-Ewald for long-range electrostatics, the contribution (ΔG(P-M)) due to the use of a particle rather than molecule based summation scheme in real space is found to be significant, as pointed out by Hünenberger and co-workers. For GSBP, when the inner region is close to be charge neutral, the key correction is the overpolarization of water molecules at the inner/outer dielectric boundary; the magnitude of the correction (ΔG(s-pol)), however, is relatively small. For charging (oxidation) free energy in proteins, the situation is more complex, although good agreement between GSBP and PBC can still be obtained when care is exercised. The smooth dielectric boundary approximation inherent to GSBP tends to make significant errors when the inner region is featured with a high net charge. However, the error can be corrected with Poisson-Boltzmann calculations using snapshots from GSBP simulations in a straightforward and robust manner. Because of the more complex charge and solvent distributions, the magnitudes of ΔG(P-M) and ΔG(s-pol) in protein simulations appear to be different from those derived for solution simulations, leading to uncertainty in directly comparing absolute charging free energies from PBC and GSBP simulations for protein systems. The relative charging/oxidation free energies, however, are robust. With the

  16. Infrared and Raman spectra, theoretical calculations, conformations, and two-dimensional potential energy surface of 2-cyclopenten-1-one ethylene ketal.

    PubMed

    Sheu, Hong-Li; Meinander, Niklas; Laane, Jaan

    2015-03-01

    The infrared and Raman spectra of the bicyclic spiro molecule 2-cyclopenten-1-one ethylene ketal (CEK) have been recorded. Density functional theory (DFT) calculations were used to compute the theoretical spectra, and these agree well with the experimental spectra. The structures and conformational energies for the two pairs of conformational minima, which can be defined in terms of ring-bending (x) and ring-twisting (τ) vibrational coordinates, have also been calculated. Utilizing the results from ab initio MP2/cc-PVTZ computations, a two-dimensional potential energy surface (PES) was calculated. The energy levels and wave functions for this PES were then calculated, and the characteristics of these were analyzed. At lower energies, all of the quantum states are doubly degenerate and correspond to either the lower-energy conformation L or to conformation H, which is 154 cm(-1) higher in energy. At energies above the barrier to interconversion of 264 cm(-1), the wave functions show that the quantum levels have significant probabilities for both conformations. PMID:25133325

  17. Biogas - the calculable energy

    NASA Astrophysics Data System (ADS)

    Kith, Károly; Nagy, Orsolya; Balla, Zoltán; Tamás, András

    2015-04-01

    EU actions against climate change are rising energy prices, both have emphasized the use of renewable energy,increase investments and energy efficiency. A number of objectives formulated in the EC decree no. 29/2009 by 2020. This document is based on the share of renewable energies in energy consumption should be increased to 20% (EC, 2009). The EU average is 20% but the share of renewables vary from one member state to another. In Hungary in 2020, 14.65% renewable energy share is planned to be achieved. According to the latest Eurostat data, the share of renewable energy in energy consumption of the EU average was 14.1%, while in Hungary, this share was 9.6% in 2012. (EUROSTAT, 2014). The use of renewable energy plant level is influenced by several factors. The most important of these is the cost savings and efficiency gains. Hungarian investments in renewable energy production usually have high associated costs and the payback period is substantially more than five years, depending on the support rate. For example, the payback period is also influenced by the green electricity generated feed prices, which is one of the lowest in Hungary compared the Member States of the European Union. Consequently, it is important to increase the production of green energy. Nowadays, predictable biogas energy is an outstanding type of decentralized energy production. It follows directly that agricultural by-products can be used to produce energy and they also create jobs by the construction of a biogas plant. It is important to dispose of and destroy hazardous and noxious substances in energy production. It follows from this that the construction of biogas plants have a positive impact, in addition to green energy which is prepared to reduce the load on the environment. The production of biogas and green electricity is one of the most environment friendly forms of energy production. Biogas production also has other important ecological effects, such as the substitution of

  18. Prebiotic Atmospheric Chemistry on Titan: Formation Kinetics via Ab Initio Calculations for Potential Energy Surface (PES) Mapping

    NASA Astrophysics Data System (ADS)

    Gonzalez, Dayana; Mebel, Alexander

    2016-03-01

    It has been recently shown that Titan provides a unique perspective in our solar system: its atmosphere is comparable to a model of prebiotic Earth's. Provided the organic cationic and anionic molecular species identified by the Cassini spacecraft, this research characterizes reaction pathways for the reactions of methyl derivatives of the cyclopropenyl cation, the methyl cation with methyl- and dimethyl-acetylene, and reactions of resonance structures of protonated acrylonitrile with CH2NH. Isomerization and dissociation reactions involving methyl-cyclopropenyl cations, the perinaphthenyl cation and anion, and cations of pyrimidine and purine precursors of nucleobases will be examined to locate reaction pathways, intermediates, transition states, and products of the reactions. Gaussian '09 software is used for ab initio calculations to map out the PES. Geometry optimizations and vibrational frequency computations are preformed via the double-hybrid density functional B2PLYP-D3. Single-point energies are refined by use of the explicitly-correlated coupled-cluster CCSD(T)-F12 method. Rate constants are calculated using microcanonical RRKM theory, and pressure effects evaluated used the Master Equation approach; these allow for prediction of absolute rate constants and product branching ratios at different pressures and temperatures.

  19. Parameterised local spin density exchange-correlation energies and potentials for electronic structure calculations I. Zero temperature formalism

    NASA Astrophysics Data System (ADS)

    MacLaren, J. M.; Clougherty, D. P.; McHenry, M. E.; Donovan, M. M.

    1991-09-01

    Commonly used approximate forms for the exchange-correlation energy and potential within the local density approximation are summarised, and FORTRAN code is included for the evaluation of these various forms. Included are the following: Xα, Kohn-Sham-Gaspàr, Hedin-Lundqvist-Wilkins, Janak-Moruzzi-Williams, Von Barth-Hedin, Ceperley-Alder (Perdew-Zunger), and Ceperley-Alder (Vosko-Wilk-Nusair). Both the Vosko-Wilk-Nusair and the Von Barth-Hedin expressions for spin interpolation between paramagnetic and ferromagnetic limits are also provided.

  20. Calculation of state energy of (2 n+1)-fold wells using the spectral properties of supersymmetry shape-invariant potential

    NASA Astrophysics Data System (ADS)

    Tavakkoli, Marjan

    2013-02-01

    Shape invariance is an important factor of many exactly solvable quantum mechanics. Several examples of shape-invariant `discrete quantum mechanical systems' are introduced and discussed in some detail. We present the spectral properties of supersymmetric shape-invariant potentials (SIP). Here we are interested in some time-independent integrable systems which are exactly solvable owing to the existence of supersymmetric shape-invariant symmetry. In 1981 Witten proposed (0+1)-dimensional limit of supersymmetry (SUSY) quantum field theory, where the supercharges of SUSY quantum mechanics generate transformation between two orthogonal eigenstates of a given Hamiltonian wit degenerate eigenvaluesfor the non-SIP as very few lower eigenvalues can be known analytically, which are small to calculate spectral fluctuation.

  1. Communication: A new ab initio potential energy surface for HCl-H2O, diffusion Monte Carlo calculations of D0 and a delocalized zero-point wavefunction

    NASA Astrophysics Data System (ADS)

    Mancini, John S.; Bowman, Joel M.

    2013-03-01

    We report a global, full-dimensional, ab initio potential energy surface describing the HCl-H2O dimer. The potential is constructed from a permutationally invariant fit, using Morse-like variables, to over 44 000 CCSD(T)-F12b/aug-cc-pVTZ energies. The surface describes the complex and dissociated monomers with a total RMS fitting error of 24 cm-1. The normal modes of the minima, low-energy saddle point and separated monomers, the double minimum isomerization pathway and electronic dissociation energy are accurately described by the surface. Rigorous quantum mechanical diffusion Monte Carlo (DMC) calculations are performed to determine the zero-point energy and wavefunction of the complex and the separated fragments. The calculated zero-point energies together with a De value calculated from CCSD(T) with a complete basis set extrapolation gives a D0 value of 1348 ± 3 cm-1, in good agreement with the recent experimentally reported value of 1334 ± 10 cm-1 [B. E. Casterline, A. K. Mollner, L. C. Ch'ng, and H. Reisler, J. Phys. Chem. A 114, 9774 (2010), 10.1021/jp102532m]. Examination of the DMC wavefunction allows for confident characterization of the zero-point geometry to be dominant at the C2v double-well saddle point and not the Cs global minimum. Additional support for the delocalized zero-point geometry is given by numerical solutions to the 1D Schrödinger equation along the imaginary-frequency out-of-plane bending mode, where the zero-point energy is calculated to be 52 cm-1 above the isomerization barrier. The D0 of the fully deuterated isotopologue is calculated to be 1476 ± 3 cm-1, which we hope will stand as a benchmark for future experimental work.

  2. Full-dimensional quantum calculations of vibrational levels of NH4+ and isotopomers on an accurate ab initio potential energy surface

    DOE PAGES

    Hua -Gen Yu; Han, Huixian; Guo, Hua

    2016-03-29

    Vibrational energy levels of the ammonium cation (NH4+) and its deuterated isotopomers are calculated using a numerically exact kinetic energy operator on a recently developed nine-dimensional permutation invariant semiglobal potential energy surface fitted to a large number of high-level ab initio points. Like CH4, the vibrational levels of NH4+ and ND4+ exhibit a polyad structure, characterized by a collective quantum number P = 2(v1 + v3) + v2 + v4. As a result, the low-lying vibrational levels of all isotopomers are assigned and the agreement with available experimental data is better than 1 cm–1.

  3. Full-Dimensional Quantum Calculations of Vibrational Levels of NH4(+) and Isotopomers on An Accurate Ab Initio Potential Energy Surface.

    PubMed

    Yu, Hua-Gen; Han, Huixian; Guo, Hua

    2016-04-14

    Vibrational energy levels of the ammonium cation (NH4(+)) and its deuterated isotopomers are calculated using a numerically exact kinetic energy operator on a recently developed nine-dimensional permutation invariant semiglobal potential energy surface fitted to a large number of high-level ab initio points. Like CH4, the vibrational levels of NH4(+) and ND4(+) exhibit a polyad structure, characterized by a collective quantum number P = 2(v1 + v3) + v2 + v4. The low-lying vibrational levels of all isotopomers are assigned and the agreement with available experimental data is better than 1 cm(-1).

  4. Free-energy calculations using classical molecular simulation: application to the determination of the melting point and chemical potential of a flexible RDX model.

    PubMed

    Sellers, Michael S; Lísal, Martin; Brennan, John K

    2016-03-21

    We present an extension of various free-energy methodologies to determine the chemical potential of the solid and liquid phases of a fully-flexible molecule using classical simulation. The methods are applied to the Smith-Bharadwaj atomistic potential representation of cyclotrimethylene trinitramine (RDX), a well-studied energetic material, to accurately determine the solid and liquid phase Gibbs free energies, and the melting point (Tm). We outline an efficient technique to find the absolute chemical potential and melting point of a fully-flexible molecule using one set of simulations to compute the solid absolute chemical potential and one set of simulations to compute the solid-liquid free energy difference. With this combination, only a handful of simulations are needed, whereby the absolute quantities of the chemical potentials are obtained, for use in other property calculations, such as the characterization of crystal polymorphs or the determination of the entropy. Using the LAMMPS molecular simulator, the Frenkel and Ladd and pseudo-supercritical path techniques are adapted to generate 3rd order fits of the solid and liquid chemical potentials. Results yield the thermodynamic melting point Tm = 488.75 K at 1.0 atm. We also validate these calculations and compare this melting point to one obtained from a typical superheated simulation technique. PMID:26661376

  5. Free-energy calculations using classical molecular simulation: application to the determination of the melting point and chemical potential of a flexible RDX model.

    PubMed

    Sellers, Michael S; Lísal, Martin; Brennan, John K

    2016-03-21

    We present an extension of various free-energy methodologies to determine the chemical potential of the solid and liquid phases of a fully-flexible molecule using classical simulation. The methods are applied to the Smith-Bharadwaj atomistic potential representation of cyclotrimethylene trinitramine (RDX), a well-studied energetic material, to accurately determine the solid and liquid phase Gibbs free energies, and the melting point (Tm). We outline an efficient technique to find the absolute chemical potential and melting point of a fully-flexible molecule using one set of simulations to compute the solid absolute chemical potential and one set of simulations to compute the solid-liquid free energy difference. With this combination, only a handful of simulations are needed, whereby the absolute quantities of the chemical potentials are obtained, for use in other property calculations, such as the characterization of crystal polymorphs or the determination of the entropy. Using the LAMMPS molecular simulator, the Frenkel and Ladd and pseudo-supercritical path techniques are adapted to generate 3rd order fits of the solid and liquid chemical potentials. Results yield the thermodynamic melting point Tm = 488.75 K at 1.0 atm. We also validate these calculations and compare this melting point to one obtained from a typical superheated simulation technique.

  6. Theoretical characterization of the potential energy surface for H + N2 yields HN2. III - Calculations for the excited state surfaces

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    1991-01-01

    Additional calculations which characterize potential energy sources (PESs) for the excited 3A-double-prime state, for a bound 2(2A-prime) state, for HN2(+), and for the Rydberg states associated with HN2(+). It is anticipated that these excited state PESs will be important in interpreting and designing experiments to characterize the ground state HN2 species via neutralized ion beam techniques.

  7. On calculating the potential vorticity flux

    SciTech Connect

    Hsu, Pei-Chun; Diamond, P. H.

    2015-03-15

    We discuss and compare different approaches to calculating the dynamics of anisotropic flow structure formation in quasi two-dimensional turbulence based on potential vorticity (PV) transport in real space. The general structure of the PV flux in the relaxation processes is deduced non-perturbatively. The transport coefficients of the PV flux are then systematically calculated using perturbation theory. We develop two non-perturbative relaxation models: the first is a mean field theory for the dynamics of minimum enstrophy relaxation based on the requirement that the mean flux of PV dissipates total potential enstrophy but conserves total fluid kinetic energy. The results show that the structure of PV flux has the form of a sum of a positive definite hyper-viscous and a negative or positive viscous flux of PV. Turbulence spreading is shown to be related to PV mixing via the link of turbulence energy flux to PV flux. In the relaxed state, the ratio of the PV gradient to zonal flow velocity is homogenized. This homogenized quantity sets a constraint on the amplitudes of PV and zonal flow in the relaxed state. The second relaxation model is derived from symmetry principles alone. The form of PV flux contains a nonlinear convective term in addition to viscous and hyper-viscous terms. For both cases, the transport coefficients are calculated using perturbation theory. For a broad turbulence spectrum, a modulational calculation of the PV flux gives both a negative viscosity and a positive hyper-viscosity. For a narrow turbulence spectrum, the result of a parametric instability analysis shows that PV transport is also convective. In both relaxation and perturbative analyses, it is shown that turbulent PV transport is sensitive to flow structure, and the transport coefficients are nonlinear functions of flow shear.

  8. Full-dimensional quantum calculations of ground-state tunneling splitting of malonaldehyde using an accurate ab initio potential energy surface.

    PubMed

    Wang, Yimin; Braams, Bastiaan J; Bowman, Joel M; Carter, Stuart; Tew, David P

    2008-06-14

    Quantum calculations of the ground vibrational state tunneling splitting of H-atom and D-atom transfer in malonaldehyde are performed on a full-dimensional ab initio potential energy surface (PES). The PES is a fit to 11 147 near basis-set-limit frozen-core CCSD(T) electronic energies. This surface properly describes the invariance of the potential with respect to all permutations of identical atoms. The saddle-point barrier for the H-atom transfer on the PES is 4.1 kcalmol, in excellent agreement with the reported ab initio value. Model one-dimensional and "exact" full-dimensional calculations of the splitting for H- and D-atom transfer are done using this PES. The tunneling splittings in full dimensionality are calculated using the unbiased "fixed-node" diffusion Monte Carlo (DMC) method in Cartesian and saddle-point normal coordinates. The ground-state tunneling splitting is found to be 21.6 cm(-1) in Cartesian coordinates and 22.6 cm(-1) in normal coordinates, with an uncertainty of 2-3 cm(-1). This splitting is also calculated based on a model which makes use of the exact single-well zero-point energy (ZPE) obtained with the MULTIMODE code and DMC ZPE and this calculation gives a tunneling splitting of 21-22 cm(-1). The corresponding computed splittings for the D-atom transfer are 3.0, 3.1, and 2-3 cm(-1). These calculated tunneling splittings agree with each other to within less than the standard uncertainties obtained with the DMC method used, which are between 2 and 3 cm(-1), and agree well with the experimental values of 21.6 and 2.9 cm(-1) for the H and D transfer, respectively.

  9. Ab initio calculation of a global potential, vibrational energies, and wave functions for HCN/HNC, and a simulation of the (A-tilde)-(X-tilde) emission spectrum

    NASA Technical Reports Server (NTRS)

    Bowman, Joel M.; Gazdy, Bela; Bentley, Joseph A.; Lee, Timothy J.; Dateo, Christopher E.

    1993-01-01

    A potential energy surface for the HCN/HNC system which is a fit to extensive, high-quality ab initio, coupled-cluster calculations is presented. All HCN and HNC states with energies below the energy of the first delocalized state are reported and characterized. Vibrational transition energies are compared with all available experimental data on HCN and HNC, including high CH-overtone states up to 23,063/cm. A simulation of the (A-tilde)-(X-tilde) stimulated emission pumping (SEP) spectrum is also reported, and the results are compared to experiment. Franck-Condon factors are reported for odd bending states of HCN, with one quantum of vibrational angular momentum, in order to compare with the recent assignment by Jonas et al. (1992), on the basis of axis-switching arguments of a number of previously unassigned states in the SEP spectrum.

  10. New XDM-corrected potential energy surfaces for Ar–NO(X{sup 2}Π): A comparison with CCSD(T) calculations and experiments

    SciTech Connect

    Warehime, Michael; Johnson, Erin R.; Kłos, Jacek

    2015-01-14

    We report new potential energy surfaces for the ground state Ar–NO(X{sup 2}Π) van der Waals system calculated using the unrestricted Hartree-Fock (UHF) method with the addition of the Becke-Roussel correlation functional and exchange-hole dipole moment dispersion correction (XDM). We compare UHFBR-XDM surfaces and those previously reported by Alexander from coupled cluster CCSD(T) calculations [J. Chem. Phys. 111, 7426 (1999)]. The bound states of Ar–NO have been investigated with these new UHFBR-XDM surfaces, including relative energy-level spacing, adiabatic bender states and wave functions, and spectroscopic data. These results have been found to be in good agreement with calculations based on the CCSD(T) PESs. These new PESs are used to investigate the inelastic scattering of NO(X) by Ar. Full close-coupling integral cross sections at collision energies of 442 cm{sup −1}, 1774 cm{sup −1} and differential cross sections at collision energy of 530 cm{sup −1} were determined for transitions out of the lowest NO(X) rotational level (j = ω = 1/2,f). These cross sections are in good agreement with those calculated with CCSD(T) and accordingly in good agreement with the most recent initial and final state resolved experimental data. The UHFBR-XDM scheme yields high-quality potential surfaces with computational cost comparable to the Hartree-Fock method and our results may serve as a benchmark for application of this scheme to collisions between larger molecules.

  11. Calculation of total free energy yield as an alternative approach for predicting the importance of potential chemolithotrophic reactions in geothermal springs.

    PubMed

    Dodsworth, Jeremy A; McDonald, Austin I; Hedlund, Brian P

    2012-08-01

    To inform hypotheses regarding the relative importance of chemolithotrophic metabolisms in geothermal environments, we calculated free energy yields of 26 chemical reactions potentially supporting chemolithotrophy in two US Great Basin hot springs, taking into account the effects of changing reactant and product activities on the Gibbs free energy as each reaction progressed. Results ranged from 1.2 × 10(-5) to 3.6 J kg(-1) spring water, or 3.7 × 10(-5) to 11.5 J s(-1) based on measured flow rates, with aerobic oxidation of CH(4) or NH4 + giving the highest average yields. Energy yields calculated without constraining pH were similar to those at constant pH except for reactions where H(+) was consumed, which often had significantly lower yields when pH was unconstrained. In contrast to the commonly used normalization of reaction chemical affinities per mole of electrons transferred, reaction energy yields for a given oxidant varied by several orders of magnitude and were more sensitive to differences in the activities of products and reactants. The high energy yield of aerobic ammonia oxidation is consistent with previous observations of significant ammonia oxidation rates and abundant ammonia-oxidizing archaea in sediments of these springs. This approach offers an additional lens through which to view the thermodynamic landscape of geothermal springs.

  12. Calculation of total free energy yield as an alternative approach for predicting the importance of potential chemolithotrophic reactions in geothermal springs.

    PubMed

    Dodsworth, Jeremy A; McDonald, Austin I; Hedlund, Brian P

    2012-08-01

    To inform hypotheses regarding the relative importance of chemolithotrophic metabolisms in geothermal environments, we calculated free energy yields of 26 chemical reactions potentially supporting chemolithotrophy in two US Great Basin hot springs, taking into account the effects of changing reactant and product activities on the Gibbs free energy as each reaction progressed. Results ranged from 1.2 × 10(-5) to 3.6 J kg(-1) spring water, or 3.7 × 10(-5) to 11.5 J s(-1) based on measured flow rates, with aerobic oxidation of CH(4) or NH4 + giving the highest average yields. Energy yields calculated without constraining pH were similar to those at constant pH except for reactions where H(+) was consumed, which often had significantly lower yields when pH was unconstrained. In contrast to the commonly used normalization of reaction chemical affinities per mole of electrons transferred, reaction energy yields for a given oxidant varied by several orders of magnitude and were more sensitive to differences in the activities of products and reactants. The high energy yield of aerobic ammonia oxidation is consistent with previous observations of significant ammonia oxidation rates and abundant ammonia-oxidizing archaea in sediments of these springs. This approach offers an additional lens through which to view the thermodynamic landscape of geothermal springs. PMID:22443686

  13. Collisional excitation of NH(X{sup 3}Σ{sup −}) by Ne: Potential energy surface, scattering calculations, and comparison with experiments

    SciTech Connect

    Bouhafs, Nezha; Lique, François

    2015-11-14

    We present a new three-dimensional potential energy surface (PES) for the NH(X{sup 3}Σ{sup −})–Ne van der Waals system, which explicitly takes into account the NH vibrational motion. Ab initio calculations of the NH–Ne PES were carried out using the open-shell single- and double-excitation coupled cluster approach with non-iterative perturbational treatment of triple excitations [RCCSD(T)]. The augmented correlation-consistent quadruple zeta (aug-cc-pVQZ) basis set was employed. Mid-bond functions were also included in order to improve the accuracy in the van der Waals well. Using this new PES, we have studied the collisional excitation of NH(X{sup 3}Σ{sup −}) by Ne. Close-coupling calculations of the collisional excitation cross sections of the fine-structure levels of NH by Ne are performed for energies up to 3000 cm{sup −1}, which yield, after thermal average, rate coefficients up to 350 K. The propensity rules between fine-structure levels are reported, and it is found that F-conserving cross sections are larger than F-changing cross sections even if the propensity rules are not as strong as for the NH–He system. The calculated rate coefficients are compared with available experimental measurements at room temperature and a fairly good agreement is found between experimental and theoretical data, confirming the good quality of the scattering calculations and also the accuracy of the potential energy surface used in this work.

  14. Quantum Tunneling in Testosterone 6β-Hydroxylation by Cytochrome P450: Reaction Dynamics Calculations Employing Multiconfiguration Molecular-Mechanical Potential Energy Surfaces

    NASA Astrophysics Data System (ADS)

    Zhang, Yan; Lin, Hai

    2009-05-01

    Testosterone hydroxylation is a prototypical reaction of human cytochrome P450 3A4, which metabolizes about 50% of oral drugs on the market. Reaction dynamics calculations were carried out for the testosterone 6β-hydrogen abstraction and the 6β-d1-testosterone 6β-duterium abstraction employing a model that consists of the substrate and the active oxidant compound I. The calculations were performed at the level of canonical variational transition state theory with multidimensional tunneling and were based on a semiglobal full-dimensional potential energy surface generated by the multiconfiguration molecular mechanics technique. The tunneling coefficients were found to be around 3, indicating substantial contributions by quantum tunneling. However, the tunneling made only modest contributions to the kinetic isotope effects. The kinetic isotope effects were computed to be about 2 in the doublet spin state and about 5 in the quartet spin state.

  15. Electrostatic potential and Born energy of charged molecules interacting with phospholipid membranes: calculation via 3-D numerical solution of the full Poisson equation.

    PubMed

    Schnitzer, J E; Lambrakis, K C

    1991-09-21

    Understanding the physicochemical basis of the interaction of molecules with lipid bilayers is fundamental to membrane biology. In this study, a new, three-dimensional numerical solution of the full Poisson equation including local dielectric variation is developed using finite difference techniques in order to model electrostatic interactions of charged molecules with a non-uniform dielectric. This solution is used to describe the electric field and electrostatic potential profile of a charged molecule interacting with a phospholipid bilayer in a manner consistent with the known composition and structure of the membrane. Furthermore, the Born interaction energy is then calculated by appropriate integration of the electric field over whole space. Numerical computations indicate that the electrostatic potential profile surrounding a charge molecule and its resultant Born interaction energy are a function of molecular position within the membrane and change most significantly within the polar region of the bilayer. The maximum interaction energy is observed when the charge is placed at the center of the hydrophobic core of the membrane and is strongly dependent on the size of the charge and on the thickness of the hydrocarbon core of the bilayer. The numerical results of this continuum model are compared with various analytical approximations for the Born energy including models established for discontinuous slab dielectrics. The calculated energies agree with the well-known Born analytical expression only when the charge is located near the center of a hydrocarbon core of greater than 60 A in thickness. The Born-image model shows excellent agreement with the numerical results only when modified to include an appropriate effective thickness of the low dielectric region. In addition, a newly derived approximation which considers the local mean dielectric provides a simple and continuous solution that also agrees well with the numerical results.

  16. The hydrogen abstraction reaction O(3P) + CH4: a new analytical potential energy surface based on fit to ab initio calculations.

    PubMed

    González-Lavado, Eloisa; Corchado, Jose C; Espinosa-Garcia, Joaquin

    2014-02-14

    Based exclusively on high-level ab initio calculations, a new full-dimensional analytical potential energy surface (PES-2014) for the gas-phase reaction of hydrogen abstraction from methane by an oxygen atom is developed. The ab initio information employed in the fit includes properties (equilibrium geometries, relative energies, and vibrational frequencies) of the reactants, products, saddle point, points on the reaction path, and points on the reaction swath, taking especial caution respecting the location and characterization of the intermediate complexes in the entrance and exit channels. By comparing with the reference results we show that the resulting PES-2014 reproduces reasonably well the whole set of ab initio data used in the fitting, obtained at the CCSD(T) = FULL/aug-cc-pVQZ//CCSD(T) = FC/cc-pVTZ single point level, which represents a severe test of the new surface. As a first application, on this analytical surface we perform an extensive dynamics study using quasi-classical trajectory calculations, comparing the results with recent experimental and theoretical data. The excitation function increases with energy (concave-up) reproducing experimental and theoretical information, although our values are somewhat larger. The OH rotovibrational distribution is cold in agreement with experiment. Finally, our results reproduce experimental backward scattering distribution, associated to a rebound mechanism. These results lend confidence to the accuracy of the new surface, which substantially improves the results obtained with our previous surface (PES-2000) for the same system.

  17. Calculation of the structure, potential energy surface, vibrational dynamics, and electric dipole properties for the Xe:HI van der Waals complex.

    PubMed

    Preller, M; Grunenberg, J; Bulychev, V P; Bulanin, M O

    2011-05-01

    We report the structure and spectroscopic characteristics for the Xe:HI van der Waals binary isomers determined from variational solutions of two-dimensional and three-dimensional (3D) vibrational Schrödinger equations. The solutions are based on a potential energy surface computed at the coupled-cluster level of theory including single and double excitations and a non-iterative perturbation treatment of triple excitations [CCSD(T)]. The dipole moment surface was calculated using quadratic configuration interaction (QCISD). The global potential minimum is shown to be located at the anti-hydrogen-bonded Xe-IH isomer, 21 cm(-1) below the secondary local minimum associated with the hydrogen-bonded Xe-HI isomeric form. The dissociation energy from the global minimum is 245.9 cm(-1). 3D Schrödinger equations are solved for the rotational quantum numbers J = k = 0, 1, and 2, without invoking an adiabatic separation of high- and low-frequency degrees of freedom. The vibrational ground state resides in the Xe-HI potential well, while the first excited state, 8.59 cm(-1) above the ground, occupies the Xe-IH well. We find that intra-complex dynamics exhibits a sudden transformation upon increase of the r(HI) bond length, accompanied by abrupt changes in the geometric and dipole parameters. A similar chaotic behavior is predicted to occur for Xe:DI at a shorter r(DI) bond length, which implies stronger coupling between low- and high-frequency motions in the heavier complex. Our calculations confirm a strong enhancement for the r(HI) stretch fundamental and a significant weakening for the first overtone vibrational transitions in Xe:HI, as compared to those in the free HI molecule. A qualitative explanation of this, earlier experimentally detected effect is suggested.

  18. Calculation of the structure, potential energy surface, vibrational dynamics, and electric dipole properties for the Xe:HI van der Waals complex

    NASA Astrophysics Data System (ADS)

    Preller, M.; Grunenberg, J.; Bulychev, V. P.; Bulanin, M. O.

    2011-05-01

    We report the structure and spectroscopic characteristics for the Xe:HI van der Waals binary isomers determined from variational solutions of two-dimensional and three-dimensional (3D) vibrational Schrödinger equations. The solutions are based on a potential energy surface computed at the coupled-cluster level of theory including single and double excitations and a non-iterative perturbation treatment of triple excitations [CCSD(T)]. The dipole moment surface was calculated using quadratic configuration interaction (QCISD). The global potential minimum is shown to be located at the anti-hydrogen-bonded Xe-IH isomer, 21 cm-1 below the secondary local minimum associated with the hydrogen-bonded Xe-HI isomeric form. The dissociation energy from the global minimum is 245.9 cm-1. 3D Schrödinger equations are solved for the rotational quantum numbers J = k = 0, 1, and 2, without invoking an adiabatic separation of high- and low-frequency degrees of freedom. The vibrational ground state resides in the Xe-HI potential well, while the first excited state, 8.59 cm-1 above the ground, occupies the Xe-IH well. We find that intra-complex dynamics exhibits a sudden transformation upon increase of the r(HI) bond length, accompanied by abrupt changes in the geometric and dipole parameters. A similar chaotic behavior is predicted to occur for Xe:DI at a shorter r(DI) bond length, which implies stronger coupling between low- and high-frequency motions in the heavier complex. Our calculations confirm a strong enhancement for the r(HI) stretch fundamental and a significant weakening for the first overtone vibrational transitions in Xe:HI, as compared to those in the free HI molecule. A qualitative explanation of this, earlier experimentally detected effect is suggested.

  19. Calculation of the structure, potential energy surface, vibrational dynamics, and electric dipole properties for the Xe:HI van der Waals complex.

    PubMed

    Preller, M; Grunenberg, J; Bulychev, V P; Bulanin, M O

    2011-05-01

    We report the structure and spectroscopic characteristics for the Xe:HI van der Waals binary isomers determined from variational solutions of two-dimensional and three-dimensional (3D) vibrational Schrödinger equations. The solutions are based on a potential energy surface computed at the coupled-cluster level of theory including single and double excitations and a non-iterative perturbation treatment of triple excitations [CCSD(T)]. The dipole moment surface was calculated using quadratic configuration interaction (QCISD). The global potential minimum is shown to be located at the anti-hydrogen-bonded Xe-IH isomer, 21 cm(-1) below the secondary local minimum associated with the hydrogen-bonded Xe-HI isomeric form. The dissociation energy from the global minimum is 245.9 cm(-1). 3D Schrödinger equations are solved for the rotational quantum numbers J = k = 0, 1, and 2, without invoking an adiabatic separation of high- and low-frequency degrees of freedom. The vibrational ground state resides in the Xe-HI potential well, while the first excited state, 8.59 cm(-1) above the ground, occupies the Xe-IH well. We find that intra-complex dynamics exhibits a sudden transformation upon increase of the r(HI) bond length, accompanied by abrupt changes in the geometric and dipole parameters. A similar chaotic behavior is predicted to occur for Xe:DI at a shorter r(DI) bond length, which implies stronger coupling between low- and high-frequency motions in the heavier complex. Our calculations confirm a strong enhancement for the r(HI) stretch fundamental and a significant weakening for the first overtone vibrational transitions in Xe:HI, as compared to those in the free HI molecule. A qualitative explanation of this, earlier experimentally detected effect is suggested. PMID:21548682

  20. Accurate free energy calculation along optimized paths.

    PubMed

    Chen, Changjun; Xiao, Yi

    2010-05-01

    The path-based methods of free energy calculation, such as thermodynamic integration and free energy perturbation, are simple in theory, but difficult in practice because in most cases smooth paths do not exist, especially for large molecules. In this article, we present a novel method to build the transition path of a peptide. We use harmonic potentials to restrain its nonhydrogen atom dihedrals in the initial state and set the equilibrium angles of the potentials as those in the final state. Through a series of steps of geometrical optimization, we can construct a smooth and short path from the initial state to the final state. This path can be used to calculate free energy difference. To validate this method, we apply it to a small 10-ALA peptide and find that the calculated free energy changes in helix-helix and helix-hairpin transitions are both self-convergent and cross-convergent. We also calculate the free energy differences between different stable states of beta-hairpin trpzip2, and the results show that this method is more efficient than the conventional molecular dynamics method in accurate free energy calculation.

  1. Comparison of energy calculation procedures

    SciTech Connect

    Kusuda, T.

    1981-08-01

    ASHRAE has developed a simplified energy-calculation procedure suitable for small calculators that applied to nonresidential buildings and includes all the essential calculation elements - climatic data, buildings construction, operational characteristics, utility system and equipment performance, and internal heat gain due to lighting, occupancy, cooking, etc. A comparison of the results predicted by the proposed method for four typical HVAC (heating, ventilation, and air conditioning) systems in an office building in Washington, DC, against the predictions of seven detailed computer-simulation programs - AXCESS, BLAST, BLDSIM, DOE-2, E-CUBE, ESAS, and TRACE - revealed that the similarity of the results depended more on which analyst employed the methods than on which methods were used.

  2. Good Practices in Free-energy Calculations

    NASA Technical Reports Server (NTRS)

    Pohorille, Andrew; Jarzynski, Christopher; Chipot, Christopher

    2013-01-01

    As access to computational resources continues to increase, free-energy calculations have emerged as a powerful tool that can play a predictive role in drug design. Yet, in a number of instances, the reliability of these calculations can be improved significantly if a number of precepts, or good practices are followed. For the most part, the theory upon which these good practices rely has been known for many years, but often overlooked, or simply ignored. In other cases, the theoretical developments are too recent for their potential to be fully grasped and merged into popular platforms for the computation of free-energy differences. The current best practices for carrying out free-energy calculations will be reviewed demonstrating that, at little to no additional cost, free-energy estimates could be markedly improved and bounded by meaningful error estimates. In energy perturbation and nonequilibrium work methods, monitoring the probability distributions that underlie the transformation between the states of interest, performing the calculation bidirectionally, stratifying the reaction pathway and choosing the most appropriate paradigms and algorithms for transforming between states offer significant gains in both accuracy and precision. In thermodynamic integration and probability distribution (histogramming) methods, properly designed adaptive techniques yield nearly uniform sampling of the relevant degrees of freedom and, by doing so, could markedly improve efficiency and accuracy of free energy calculations without incurring any additional computational expense.

  3. Ab initio calculations of stationary points on the benzene-Ar and p-difluorobenzene-Ar potential energy surfaces: barriers to bound orbiting states

    NASA Astrophysics Data System (ADS)

    Moulds, Rebecca J.; Buntine, Mark A.; Lawrance, Warren D.

    2004-09-01

    The potential energy surfaces of the van der Waals complexes benzene-Ar and p-difluorobenzene-Ar have been investigated at the second-order Møller-Plesset (MP2) level of theory with the aug-cc-pVDZ basis set. Calculations were performed with unconstrained geometry optimization for all stationary points. This study has been performed to elucidate the nature of a conflict between experimental results from dispersed fluorescence and velocity map imaging (VMI). The inconsistency is that spectra for levels of p-difluorobenzene-Ar and -Kr below the dissociation thresholds determined by VMI show bands where free p-difluorobenzene emits, suggesting that dissociation is occurring. We proposed that the bands observed in the dispersed fluorescence spectra are due to emission from states in which the rare gas atom orbits the aromatic chromophore; these states are populated by intramolecular vibrational redistribution from the initially excited level [S. M. Bellm, R. J. Moulds, and W. D. Lawrance, J. Chem. Phys. 115, 10709 (2001)]. To test this proposition, stationary points have been located on both the benzene-Ar and p-difluorobenzene-Ar potential energy surfaces (PESs) to determine the barriers to this orbiting motion. Comparison with previous single point CCSD(T) calculations of the benzene-Ar PES has been used to determine the amount by which the barriers are overestimated at the MP2 level. As there is little difference in the comparable regions of the benzene-Ar and p-difluorobenzene-Ar PESs, the overestimation is expected to be similar for p-difluorobenzene-Ar. Allowing for this overestimation gives the barrier to movement of the Ar atom around the pDFB ring via the valley between the H atoms as ⩽204 cm-1 in S0 (including zero point energy). From the estimated change upon electronic excitation, the corresponding barrier in S1 is estimated to be ⩽225 cm-1. This barrier is less than the 240 cm-1 energy of 302¯, the vibrational level for which the anomalous "free p

  4. Eight-dimensional quantum reaction rate calculations for the H+CH4 and H2+CH3 reactions on recent potential energy surfaces.

    PubMed

    Zhou, Yong; Zhang, Dong H

    2014-11-21

    Eight-dimensional (8D) transition-state wave packet simulations have been performed on two latest potential energy surfaces (PES), the Zhou-Fu-Wang-Collins-Zhang (ZFWCZ) PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)] and the Xu-Chen-Zhang (XCZ)-neural networks (NN) PES [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. Reaction rate constants for both the H+CH4 reaction and the H2+CH3 reaction are calculated. Simulations of the H+CH4 reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable high accuracy for low temperatures while leads to slightly lower results for high temperatures, in line with the distribution of interpolation error associated with the ZFWCZ PES. The 8D H+CH4 rate constants derived on the ZFWCZ PES compare well with full-dimensional 12D results based on the equivalent m-ZFWCZ PES, with a maximum relative difference of no more than 20%. Additionally, very good agreement is shown by comparing the 8D XCZ-NN rate constants with the 12D results obtained on the ZFWCZ-WM PES, after considering the difference in static barrier height between these two PESs. The reaction rate constants calculated for the H2+CH3 reaction are found to be in good consistency with experimental observations.

  5. Asymmetric hydrogen bonds in a centrosymmetric environment. III. Quantum mechanical calculations of the potential-energy surfaces for the very short hydrogen bonds in potassium hydrogen dichloromaleate.

    PubMed

    Majerz, I; Olovsson, I

    2007-10-01

    In the crystal structure of potassium hydrogen dichloromaleate there are two short hydrogen bonds of 2.44 A. The 'heavy-atom' structure is centrosymmetric (space group P1) with centers of symmetry in the middle of the O-O bonds, suggesting centered hydrogen bonds. However, earlier unconventional types of refinements of the extensive neutron data taken at 30, 90, 135, 170 and 295 K demonstrated that the H atoms are actually non-centered in the hydrogen bonds, although the environment is centrosymmetric. Traditionally it has been assumed that the hydrogen distribution adopts the same symmetry as the environment. Reviewing these unusual results it was considered of great interest to verify that the non-centered locations of the H atoms are reasonable from an energy point of view. Quantum mechanical calculations have now been carried out for the potential-energy surfaces (PES) for both the centered and non-centered locations of the H atoms. In all cases the non-centered positions are closer to the energy minima in the PES than the centered positions, and this result confirms that the structure is best described with non-centered H atoms. There is virtually perfect agreement between the quantum-mechanically derived reaction coordinates (QMRC) and the bond-order reaction coordinates (BORC) derived using Pauling's bond-order concept together with the principle of conservation of bond order. [Part I: Olovsson et al. (2001). Acta Cryst. B57, 311-316; Part II: Olovsson et al. (2002). Acta Cryst. B58, 627-631.].

  6. Calculating Standard Reduction Potentials of [4Fe–4S] Proteins

    SciTech Connect

    Perrin, Bradley S.; Niu, Shuqiang; Ichiye, Toshiko

    2013-03-15

    The oxidation–reduction potentials of electron transfer proteins determine the driving forces for their electron transfer reactions. Although the type of redox site determines the intrinsic energy required to add or remove an electron, the electrostatic interaction energy between the redox site and its surrounding environment can greatly shift the redox potentials. Here, a method for calculating the reduction potential versus the standard hydrogen electrode, E°, of a metalloprotein using a combinatio of density functional theory and continuum electrostatics is presented. This work focuses on the methodology for the continuum electrostatics calculations, including various factors that may affect the accuracy. The calculations are demonstrated using crystal structures of six homologous HiPIPs, which give E° that are in excellent agreement with experimental results.

  7. Calculating the potential to emit particulate matter

    SciTech Connect

    Vaart, D.R. van der

    1996-09-01

    As the implementation of the 1990 amendments to the Clean Air Act, and Title V in particular, continues, questions regarding the calculation of a facility`s potential to emit continue to surface. The US Environmental Protection Agency (EPA) has provided limited guidance decisions, although many are still being made during Title V implementation. This paper discusses what is meant by PM-10 and the validity of using sieve analysis in estimating particulate emissions. Title V of the Clean Air Amendments of 1990, and the accompanying regulations in 40 CFR Part 70, defines a major source subject to Title V by calculating its potential emissions of all regulated pollutants, both criteria and hazardous air pollutants. For PM, the threshold emission rate is 100 tons per year (tpy) for applicability to Title V. Much discussion has ensued regarding a definition of PM for the purpose of determining a facility`s potential to emit. Recently, EPA provided guidance which indicated that only PM-10 should be considered for making this determination although many states regulate larger particles through their state implementation plan (SIP) as a surrogate for PM-10.

  8. A computational study of barium blockades in the KcsA potassium channel based on multi-ion potential of mean force calculations and free energy perturbation.

    PubMed

    Rowley, Christopher N; Roux, Benoît

    2013-10-01

    Electrophysiological studies have established that the permeation of Ba(2+) ions through the KcsA K(+)-channel is impeded by the presence of K(+) ions in the external solution, while no effect is observed for external Na(+) ions. This Ba(2+) "lock-in" effect suggests that at least one of the external binding sites of the KcsA channel is thermodynamically selective for K(+). We used molecular dynamics simulations to interpret these lock-in experiments in the context of the crystallographic structure of KcsA. Assuming that the Ba(2+) is bound in site S(2) in the dominant blocked state, we examine the conditions that could impede its translocation and cause the observed "lock-in" effect. Although the binding of a K(+) ion to site S(1) when site S(2) is occupied by Ba(2+) is prohibitively high in energy (>10 kcal/mol), binding to site S0 appears to be more plausible (ΔG > 4 kcal/mol). The 2D potential of mean force (PMF) for the simultaneous translocation of Ba(2+) from site S(2) to site S(1) and of a K(+) ion on the extracellular side shows a barrier that is consistent with the concept of external lock-in. The barrier opposing the movement of Ba(2+) is very high when a cation is in site S(0), and considerably smaller when the site is unoccupied. Furthermore, free energy perturbation calculations show that site S(0) is selective for K(+) by 1.8 kcal/mol when S(2) is occupied by Ba(2+). However, the same site S(0) is nonselective when site S(2) is occupied by K(+), which shows that the presence of Ba(2+) affects the selectivity of the pore. A theoretical framework within classical rate theory is presented to incorporate the concentration dependence of the external ions on the lock-in effect.

  9. Explicitly correlated MRCI-F12 potential energy surfaces for methane fit with several permutation invariant schemes and full-dimensional vibrational calculations

    NASA Astrophysics Data System (ADS)

    Majumder, Moumita; Hegger, Samuel E.; Dawes, Richard; Manzhos, Sergei; Wang, Xiao-Gang; Tucker, Carrington, Jr.; Li, Jun; Guo, Hua

    2015-07-01

    A data-set of nearly 100,000 symmetry unique multi-configurational ab initio points for methane were generated at the (AE)-MRCI-F12(Q)/CVQZ-F12 level, including energies beyond 30,000 cm-1 above the minimum and fit into potential energy surfaces (PESs) by several permutation invariant schemes. A multi-expansion interpolative fit combining interpolating moving least squares (IMLS) fitting and permutation invariant polynomials (PIP) was able to fit the complete data-set to a root-mean-square deviation of 1.0 cm-1 and thus was used to benchmark the other fitting methods. The other fitting methods include a single PIP expansion and two neural network (NN) based approaches, one of which combines NN with PIP. Full-dimensional variational vibrational calculations using a contracted-iterative method (and a Lanczos eigensolver) were used to assess the spectroscopic accuracy of the electronic structure method. The results show that the NN-based fitting approaches are able to fit the data-set remarkably accurately with the PIP-NN method producing levels in remarkably close agreement with the PIP-IMLS benchmark. The (AE)-MRCI-F12(Q)/CVQZ-F12 electronic structure method produces vibrational levels of near spectroscopic accuracy and a superb equilibrium geometry. The levels are systematically slightly too high, beginning at ∼ 1-2 cm-1 above the fundamentals and becoming correspondingly higher for overtones. The PES is therefore suitable for small ab initio or empirical corrections and since it is based on a multi-reference method, can be extended to represent dynamically relevant dissociation channels.

  10. A computational study of barium blockades in the KcsA potassium channel based on multi-ion potential of mean force calculations and free energy perturbation

    PubMed Central

    Rowley, Christopher N.

    2013-01-01

    Electrophysiological studies have established that the permeation of Ba2+ ions through the KcsA K+-channel is impeded by the presence of K+ ions in the external solution, while no effect is observed for external Na+ ions. This Ba2+ “lock-in” effect suggests that at least one of the external binding sites of the KcsA channel is thermodynamically selective for K+. We used molecular dynamics simulations to interpret these lock-in experiments in the context of the crystallographic structure of KcsA. Assuming that the Ba2+ is bound in site S2 in the dominant blocked state, we examine the conditions that could impede its translocation and cause the observed “lock-in” effect. Although the binding of a K+ ion to site S1 when site S2 is occupied by Ba2+ is prohibitively high in energy (>10 kcal/mol), binding to site S0 appears to be more plausible (ΔG > 4 kcal/mol). The 2D potential of mean force (PMF) for the simultaneous translocation of Ba2+ from site S2 to site S1 and of a K+ ion on the extracellular side shows a barrier that is consistent with the concept of external lock-in. The barrier opposing the movement of Ba2+ is very high when a cation is in site S0, and considerably smaller when the site is unoccupied. Furthermore, free energy perturbation calculations show that site S0 is selective for K+ by 1.8 kcal/mol when S2 is occupied by Ba2+. However, the same site S0 is nonselective when site S2 is occupied by K+, which shows that the presence of Ba2+ affects the selectivity of the pore. A theoretical framework within classical rate theory is presented to incorporate the concentration dependence of the external ions on the lock-in effect. PMID:24043859

  11. Full-dimensional quantum calculations of the dissociation energy, zero-point, and 10 K properties of H7+/D7+ clusters using an ab initio potential energy surface

    NASA Astrophysics Data System (ADS)

    Barragán, Patricia; Pérez de Tudela, Ricardo; Qu, Chen; Prosmiti, Rita; Bowman, Joel M.

    2013-07-01

    Diffusion Monte Carlo (DMC) and path-integral Monte Carlo computations of the vibrational ground state and 10 K equilibrium state properties of the H_7^+/D_7^+ cations are presented, using an ab initio full-dimensional potential energy surface. The DMC zero-point energies of dissociated fragments H_5^+(D_5^+)+H2(D2) are also calculated and from these results and the electronic dissociation energy, dissociation energies, D0, of 752 ± 15 and 980 ± 14 cm-1 are reported for H_7^+ and D_7^+, respectively. Due to the known error in the electronic dissociation energy of the potential surface, these quantities are underestimated by roughly 65 cm-1. These values are rigorously determined for first time, and compared with previous theoretical estimates from electronic structure calculations using standard harmonic analysis, and available experimental measurements. Probability density distributions are also computed for the ground vibrational and 10 K state of H_7^+ and D_7^+. These are qualitatively described as a central H_3^+/D_3^+ core surrounded by "solvent" H2/D2 molecules that nearly freely rotate.

  12. Calculations of 21 Λ-S and 42 Ω states of BC molecule: Potential energy curves, spectroscopic parameters and spin-orbit coupling effect.

    PubMed

    Xing, Wei; Shi, Deheng; Sun, Jinfeng; Zhu, Zunlue

    2016-01-15

    The potential energy curves (PECs) were calculated for the 42 Ω states generated from the 21 Λ-S states (X(4)Σ(-), A(4)Π, B(4)Σ(-), a(2)Π, b(2)Σ(-), c(2)Δ, d(2)Σ(+), e(2)Π, 3(2)Π, 4(2)Π, 5(2)Π, 2(2)Σ(-), 3(2)Σ(-), 2(2)Σ(+), 3(2)Σ(+), 2(2)Δ, 3(2)Δ, 1(4)Σ(+), 2(4)Π, 1(4)Δ and 1(2)Φ), which originated from the lowest two dissociation channels, B((2)Pu)+C((3)Pg) and B((2)Pu)+C((1)Dg), of the BC molecule. The PECs were calculated for internuclear separations from 0.08 to 1.10 nm using the CASSCF method, which was followed by the icMRCI approach with the aug-cc-pV6Z basis set. Of these 21 Λ-S states, the e(2)Π, 2(2)Δ, 2(2)Σ(-), 4(2)Π, 1(2)Φ and 3(2)Δ possess the double wells. The A(4)Π, a(2)Π, c(2)Δ, 2(4)Π, 4(2)Π, 5(2)Π, 1(4)Δ and 1(2)Φ states are inverted with the spin-orbit coupling (SOC) effect taken into account. The first well of e(2)Π state and the second well of 4(2)Π and 2(2)Δ states do not have any vibrational states whether with or without the SOC effect included. All the Λ-S and Ω states involved in this paper are bound states. Scalar relativistic correction was included by the third-order Douglas-Kroll Hamiltonian approximation at the level of an aug-cc-pV5Z basis set. Core-valence correlation correction was included at the level of an aug-cc-pCV5Z basis set. The SOC effect was accounted for by the state interaction method with the Breit-Pauli Hamiltonian and the all-electron cc-pCV5Z basis set. The PECs of all the states were extrapolated to the complete basis set limit. The spectroscopic parameters were obtained. The vibrational properties of several Λ-S and Ω states with the relatively shallow wells were evaluated. The SOC effect on the spectroscopic parameters is not obvious for almost all the states. The spectroscopic properties reported in this paper can be expected to be reliably predicted ones.

  13. Calculations of 21 Λ-S and 42 Ω states of BC molecule: Potential energy curves, spectroscopic parameters and spin-orbit coupling effect

    NASA Astrophysics Data System (ADS)

    Xing, Wei; Shi, Deheng; Sun, Jinfeng; Zhu, Zunlue

    2016-01-01

    The potential energy curves (PECs) were calculated for the 42 Ω states generated from the 21 Λ-S states (X4Σ-, A4Π, B4Σ-, a2Π, b2Σ-, c2Δ, d2Σ+, e2Π, 32Π, 42Π, 52Π, 22Σ-, 32Σ-, 22Σ+, 32Σ+, 22Δ, 32Δ, 14Σ+, 24Π, 14Δ and 12Φ), which originated from the lowest two dissociation channels, B(2Pu) + C(3Pg) and B(2Pu) + C(1Dg), of the BC molecule. The PECs were calculated for internuclear separations from 0.08 to 1.10 nm using the CASSCF method, which was followed by the icMRCI approach with the aug-cc-pV6Z basis set. Of these 21 Λ-S states, the e2Π, 22Δ, 22Σ-, 42Π, 12Φ and 32Δ possess the double wells. The A4Π, a2Π, c2Δ, 24Π, 42Π, 52Π, 14Δ and 12Φ states are inverted with the spin-orbit coupling (SOC) effect taken into account. The first well of e2Π state and the second well of 42Π and 22Δ states do not have any vibrational states whether with or without the SOC effect included. All the Λ-S and Ω states involved in this paper are bound states. Scalar relativistic correction was included by the third-order Douglas-Kroll Hamiltonian approximation at the level of an aug-cc-pV5Z basis set. Core-valence correlation correction was included at the level of an aug-cc-pCV5Z basis set. The SOC effect was accounted for by the state interaction method with the Breit-Pauli Hamiltonian and the all-electron cc-pCV5Z basis set. The PECs of all the states were extrapolated to the complete basis set limit. The spectroscopic parameters were obtained. The vibrational properties of several Λ-S and Ω states with the relatively shallow wells were evaluated. The SOC effect on the spectroscopic parameters is not obvious for almost all the states. The spectroscopic properties reported in this paper can be expected to be reliably predicted ones.

  14. Comparison of the Effective Fragment Potential Method with Symmetry-Adapted Perturbation Theory in the Calculation of Intermolecular Energies for Ionic Liquids.

    PubMed

    Tan, Samuel Y S; Izgorodina, Ekaterina I

    2016-06-14

    The effective fragment potential (EFP) method that decomposes the interaction energy as a sum of the five fundamental forces-electrostatic, exchange-repulsion, polarization, dispersion, and charge transfer-was applied to a large test set of ionic liquid ion pairs and compared against the state-of-the-art method, Symmetry-Adapted Perturbation Theory (SAPT). The ion pairs include imidazolium and pyrrolidinium cations combined with anions that are routinely used in the field of ionic liquids. The aug-cc-pVDZ, aug-cc-pVTZ, and 6-311++G(d,p) basis sets were used for EFP, while SAPT2+3/aug-cc-pVDZ provided the benchmark energies. Differences between the two methods were found to be large, and strongly dependent on the anion type. For the aug-cc-pVTZ basis set, which produced the least errors, average relative errors were between 2.3% and 18.4% for pyrrolidinium ion pairs and between 2.1% and 27.7% for imidazolium ion pairs for each individual energetic component (excluding charge transfer), as well as the total interaction energy. Charge transfer gave the largest relative errors: 56% and 63% on average for pyrrolidinium- and imidazolium-based ion pairs, respectively. Scaling of the EFP components against SAPT2+3 showed improvement for polarization (induction) and dispersion terms, thus indicating potential for the development of cost-effective alternatives for intermolecular induction and dispersion potentials for ionic liquids.

  15. The hydrogen peroxide-rare gas systems: quantum chemical calculations and hyperspherical harmonic representation of the potential energy surface for atom-floppy molecule interactions.

    PubMed

    Barreto, Patricia R P; Vilela, Alessandra F A; Lombardi, Andrea; Maciel, Glauciete S; Palazzetti, Federico; Aquilanti, Vincenzo

    2007-12-13

    A quantum chemical exploration is reported on the interaction potentials of H2O2 with the rare gases, He, Ne, Ar, Kr, and Xe. Hydrogen peroxide (the simplest example of chiral molecule in its equilibrium geometry) is modeled as rigid except for the torsional mode around the O-O bond. However, on the basis of previous work (Maciel, G. S.; et al. Chem. Phys. Lett. 2006 432, 383), the internal mode description is based, rather than on the vectors of the usual valence picture, on the orthogonal local representation, which was demonstrated useful for molecular dynamics simulations, because the torsion around the vector joining the center-of-mass of the two OH radicals mimics accurately the adiabatic reaction path for chirality changing isomerization, following the torsional potential energy profile from equilibrium through the barriers for the trans and cis geometries. The basic motivation of this work is the determination of potential energy surfaces for the interactions to be used in classical and quantum simulations of molecular collisions, specifically those leading to chirality changes of possible relevance in the modeling of prebiotic phenomena. Particular attention is devoted to the definition of coordinates and expansion formulas for the potentials, allowing for a faithful representation of geometrical and symmetry properties of these systems, prototypical of the interaction of an atom with a floppy molecule.

  16. First-principles energy band calculation of Ruddlesden-Popper compound Sr3Sn2O7 using modified Becke-Johnson exchange potential

    NASA Astrophysics Data System (ADS)

    Kamimura, Sunao; Obukuro, Yuki; Matsushima, Shigenori; Nakamura, Hiroyuki; Arai, Masao; Xu, Chao-Nan

    2015-12-01

    The electronic structure of Sr3Sn2O7 is evaluated by the scalar-relativistic full potential linearized augmented plane wave (FLAPW+lo) method using the modified Becke-Johnson potential (Tran-Blaha potential) combined with the local density approximation correlation (MBJ-LDA). The fundamental gap between the valence band (VB) and conduction band (CB) is estimated to be 3.96 eV, which is close to the experimental value. Sn 5s states and Sr 4d states are predominant in the lower and upper CB, respectively. On the other hand, the lower VB is mainly composed of Sn 5s, 5p, and O 2p states, while the upper VB mainly consists of O 2p states. These features of the DOS are well reflected by the optical transition between the upper VB and lower CB, as seen in the energy dependence of the dielectric function. Furthermore, the absorption coefficient estimated from the MBJ-LDA is similar to the experimental result.

  17. An approach to optimised calculations of the potential energy surfaces for the case of electron transfer reactions at a metal/solution interface

    NASA Astrophysics Data System (ADS)

    Bronshtein, Michael D.; Nazmutdinov, Renat R.; Schmickler, Wolfgang

    2004-12-01

    An effective computational scheme to construct the adiabatic potential energy surfaces (APES) along the reaction coordinates for an electron transfer reaction occurring by two steps at a metal electrode is considered in the framework of the Anderson-Newns model. Two Theorems have been proved which predict the existence of all possible solutions of the Anderson-Newns equations at arbitrary values of the key parameters and point out the region for each solution. Asymptotic formulas for solutions near multiple roots have been derived and combined in an effective way with numerical routines. The analysis of some important properties of the APES, which can be of interest for modelling the electrochemical electron transfer processes, is presented as well. The APES describing the reduction of Zn(II) and In(III) aqua-complexes at a mercury electrode have been built and discussed.

  18. Renewable energy potential in Colombia

    NASA Astrophysics Data System (ADS)

    Correa Guzman, Jose Luis

    2008-12-01

    Renewable energy flows are very large in comparison with humankind's use of energy. In principle, all our energy needs, both now and into the future, can be met by energy from renewable sources. After many years trying to develop the alternative energy potential of Colombia, a major effort is principally being made since 2000 to explore and assess the renewable resources of the entire country. Until 2000, the availability of conventional energy sources in Colombia prevented renewable energy exploration from reaching a higher level. However, the extreme energy crisis of 1992 - 1993 alerted the authorities and the community to the necessity for exploring alternative energy sources. This energy study is a general approach to the current and future renewable energy scenario of Colombia. It was prepared in response to the increased interest around the world and in particular in Colombia to develop its non-fossil energy prospective. It, therefore, represents a working document giving an initial impression of the possible scale of the main renewables sources as a response to the concern about energy security and fossil fuel dependence problems. The assumptions made and calculations reported may therefore be subject to revision as more information becomes available. The aim of this dissertation is not only to improve the public understanding and discussion of renewable energy matters in Colombia but also to stimulate the development and application of renewable energy, wherever they have prospects of economic viability and environmental acceptability. To achieve such goal this paper reviews several renewable technologies, their availability, contribution and feasibility in Colombia.

  19. A Molecular Full-Potential LMTO Calculation for Copper Clusters

    NASA Astrophysics Data System (ADS)

    Datta, Radhika Prosad; Banerjea, Amitava; Mookerjee, Abhijit; Bhattacharyya, A. K.

    We study the electronic properties of small (10-20 atoms) copper clusters using the newly-developed molecular full-potential linearized muffin-tin orbital two-centre-fit (TCF) method of Methfessel and van Schilfgaarde. The geometric structures of the clusters had earlier been determined by us through simulated annealing using the Equivalent Crystal Theory to compute total energies. We report the variation of the binding energy, as obtained from the TCF calculations, with cluster size and compare these to the binding energies determined, for the same structures, from the ECT. We also show the variation of the HOMO-LUMO gap with cluster size, and the pseudo-density of states for select cluster sizes.

  20. Proliferation Potential of Accelerator-Drive Systems: Feasibility Calculations

    SciTech Connect

    Riendeau, C.D.; Moses, D.L.; Olson, A.P.

    1998-11-01

    Accelerator-driven systems for fissile materials production have been proposed and studied since the early 1950s. Recent advances in beam power levels for small accelerators have raised the possibility that such use could be feasible for a potential proliferator. The objective of this study is to review the state of technology development for accelerator-driven spallation neutron sources and subcritical reactors. Energy and power requirements were calculated for a proton accelerator-driven neutron spallation source and subcritical reactors to produce a significant amount of fissile material--plutonium.

  1. Spectroscopically Accurate Calculations of the Rovibrational Energies of Diatomic Hydrogen

    NASA Astrophysics Data System (ADS)

    Perry, Jason

    2005-05-01

    The Born-Oppenheimer approximation has been used to calculate the rotational and vibrational states of diatomic hydrogen. Because it is an approximation, our group now wants to use a Born-Oppenheimer potential to calculate the electronic energy that has been corrected to match closely with spectroscopic results. We are using a code that has corrections for adiabatic, relativistic, radiative, and non-adiabatic effects. The rovibrational energies have now been calculated for both bound and quasi-bound states. We also want to compute quadrupole transition probabilities for diatomic hydrogen. These calculations aspire to investigate diatomic hydrogen in astrophysical environments.

  2. An introduction to best practices in free energy calculations.

    PubMed

    Shirts, Michael R; Mobley, David L

    2013-01-01

    Free energy calculations are extremely useful for investigating small-molecule biophysical properties such as protein-ligand binding affinities and partition coefficients. However, these calculations are also notoriously difficult to implement correctly. In this chapter, we review standard methods for computing free energy via simulation, discussing current best practices and examining potential pitfalls for computational researchers performing them for the first time. We include a variety of examples and tips for how to set up and conduct these calculations, including applications to relative binding affinities and small-molecule solvation free energies.

  3. Calculation of Rydberg energy levels for the francium atom

    NASA Astrophysics Data System (ADS)

    Huang, Shi-Zhong; Chu, Jin-Min

    2010-06-01

    Based on the weakest bound electron potential model theory, the Rydberg energy levels and quantum defects of the np2Po1/2 (n = 7-50) and np2Po3/2 (n = 7-50) spectrum series for the francium atom are calculated. The calculated results are in excellent agreement with the 48 measured levels, and 40 energy levels for highly excited states are predicted.

  4. Potential Energy Curves for CO

    NASA Technical Reports Server (NTRS)

    Tobias, Irwin; Fallon, Robert J.; Vanderslice, Joseph T.

    1960-01-01

    Potential energy curves for the Chi (sup 1) Epsilon (sup plus), alpha (sup 3) II (sub r), alpha prime (sup 3) epsilon (sup plus), d (sup 3) delta, e (sup 3) Epsilon (sup minus), Alpha (sup 1) II, and Beta (sup 1) Epsilon (sup plus), electronic states of the CO molecule have been calculated by the Rydberg-Klein-Rees method. The curve for the A III state will have to bend sharply in the range between 1.9 and 2.1 angstroms or it will have to pass through a maximum to reach the proper dissociation limit.

  5. New ab initio adiabatic potential energy surfaces and bound state calculations for the singlet ground X˜ 1A1 and excited C˜ 1B2(21A') states of SO2

    NASA Astrophysics Data System (ADS)

    Kłos, Jacek; Alexander, Millard H.; Kumar, Praveen; Poirier, Bill; Jiang, Bin; Guo, Hua

    2016-05-01

    We report new and more accurate adiabatic potential energy surfaces (PESs) for the ground X˜ 1A1 and electronically excited C˜ 1B2(21A') states of the SO2 molecule. Ab initio points are calculated using the explicitly correlated internally contracted multi-reference configuration interaction (icMRCI-F12) method. A second less accurate PES for the ground X ˜ state is also calculated using an explicitly correlated single-reference coupled-cluster method with single, double, and non-iterative triple excitations [CCSD(T)-F12]. With these new three-dimensional PESs, we determine energies of the vibrational bound states and compare these values to existing literature data and experiment.

  6. Lambda-Nucleon Potential Calculated from Lattice QCD

    SciTech Connect

    Nemura, Hidekatsu

    2011-10-21

    We present our studies of Lambda-Nucleon ({Lambda}N) interaction by using lattice QCD. The equal-time Nambu-Bethe-Salpeter (NBS) amplitude of the lowest energy scattering state of a proton-{Lambda} system is calculated from lattice QCD. In this report, two different types of gauge configurations are employed: (i) Quenched QCD configurations at {beta} = 5.7 (a = 0.1416(9) fm) on a 32{sup 3}x48 lattice, whose spatial volume is (4.5 fm){sup 3}.(ii)2+1 flavor full QCD configurations generated by the PACS-CS collaboration at {beta} = 1.9 (a = 0.0907(13) fm) on a 32{sup 3}x64 lattice, whose spatial volume is (2.90 fm){sup 3}. The spin-singlet central potential is calculated from the NBS wave function for the spin J = 0 state, whereas the spin-triplet central potential as well as the tensor potential are deduced simultaneously from the NBS wave function for the spin J = 1 state by dividing it into the S-wave and the D-wave components.

  7. Wave Energy Potential in the Latvian EEZ

    NASA Astrophysics Data System (ADS)

    Beriņš, J.; Beriņš, J.; Kalnačs, J.; Kalnačs, A.

    2016-06-01

    The present article deals with one of the alternative forms of energy - sea wave energy potential in the Latvian Exclusice Economic Zone (EEZ). Results have been achieved using a new method - VEVPP. Calculations have been performed using the data on wave parameters over the past five years (2010-2014). We have also considered wave energy potential in the Gulf of Riga. The conclusions have been drawn on the recommended methodology for the sea wave potential and power calculations for wave-power plant pre-design stage.

  8. Energy and mass balance calculations for incinerators

    SciTech Connect

    Lee, C.C.; Huffman, G.L.

    1998-01-01

    Calculation of energy and mass balance within an incinerator is a very important part of designing and/or evaluating the incineration process. This article describes a simple computer model used to calculate an energy and mass balance for a rotary kiln incinerator. The main purpose of the model is to assist US Environmental Protection Agency (EPA) permit writers in evaluating the adequacy of the data submitted by applicants seeking incinerator permits. The calculation is based on the assumption that a thermodynamic equilibrium condition exits within the combustion chamber. Key parameters that the model can calculate include theoretical combustion air, excess air needed for actual combustion cases, flue gas flow rate, and exit temperature.

  9. Free-Energy Calculations. A Mathematical Perspective

    NASA Technical Reports Server (NTRS)

    Pohorille, Andrzej

    2015-01-01

    conductance, defined as the ratio of ionic current through the channel to applied voltage, can be calculated in MD simulations by way of applying an external electric field to the system and counting the number of ions that traverse the channel per unit time. If the current is small, a voltage significantly higher than the experimental one needs to be applied to collect sufficient statistics of ion crossing events. Then, the calculated conductance has to be extrapolated to the experimental voltage using procedures of unknown accuracy. Instead, we propose an alternative approach that applies if ion transport through channels can be described with sufficient accuracy by the one-dimensional diffusion equation in the potential given by the free energy profile and applied voltage. Then, it is possible to test the assumptions of the equation, recover the full voltage/current dependence, determine the reliability of the calculated conductance and reconstruct the underlying (equilibrium) free energy profile, all from MD simulations at a single voltage. We will present the underlying theory, model calculations that test this theory and simulations on ion conductance through a channel that has been extensively studied experimentally. To our knowledge this is the first case in which the complete, experimentally measured dependence of the current on applied voltage has been reconstructed from MD simulations.

  10. Monte Carlo and theoretical calculations of the first four perturbation coefficients in the high temperature series expansion of the free energy for discrete and core-softened potential models

    NASA Astrophysics Data System (ADS)

    Zhou, Shiqi; Solana, J. R.

    2013-06-01

    The first four perturbation coefficients in the expansion of the Helmholtz free energy in power series of the inverse of the reduced temperature for a number of potential models with hard-sphere cores plus core-softened and discontinuous tails are obtained from Monte Carlo simulations. The potential models considered include square-well, double square-well, and square-shoulder plus square-well, with different potential parameters. These simulation data are used to evaluate the performance of a traditional macroscopic compressibility approximation (MCA) for the second order coefficient and a recent coupling parameter series expansion (CPSE) for the first four coefficients. Comprehensive comparison indicates the incapability of the MCA for the second order coefficient in most non-stringent situations, and significance of the CPSE in accurately calculating these four coefficients.

  11. Monte Carlo and theoretical calculations of the first four perturbation coefficients in the high temperature series expansion of the free energy for discrete and core-softened potential models.

    PubMed

    Zhou, Shiqi; Solana, J R

    2013-06-28

    The first four perturbation coefficients in the expansion of the Helmholtz free energy in power series of the inverse of the reduced temperature for a number of potential models with hard-sphere cores plus core-softened and discontinuous tails are obtained from Monte Carlo simulations. The potential models considered include square-well, double square-well, and square-shoulder plus square-well, with different potential parameters. These simulation data are used to evaluate the performance of a traditional macroscopic compressibility approximation (MCA) for the second order coefficient and a recent coupling parameter series expansion (CPSE) for the first four coefficients. Comprehensive comparison indicates the incapability of the MCA for the second order coefficient in most non-stringent situations, and significance of the CPSE in accurately calculating these four coefficients.

  12. Total energy calculations and bonding at interfaces

    SciTech Connect

    Louie, S.G.

    1984-08-01

    Some of the concepts and theoretical techniques employed in recent ab initio studies of the electronic and structural properties of surfaces and interfaces are discussed. Results of total energy calculations for the 2 x 1 reconstructed diamond (111) surface and for stacking faults in Si are reviewed. 30 refs., 8 figs.

  13. Calculating Free Energies Using Average Force

    NASA Technical Reports Server (NTRS)

    Darve, Eric; Pohorille, Andrew; DeVincenzi, Donald L. (Technical Monitor)

    2001-01-01

    A new, general formula that connects the derivatives of the free energy along the selected, generalized coordinates of the system with the instantaneous force acting on these coordinates is derived. The instantaneous force is defined as the force acting on the coordinate of interest so that when it is subtracted from the equations of motion the acceleration along this coordinate is zero. The formula applies to simulations in which the selected coordinates are either unconstrained or constrained to fixed values. It is shown that in the latter case the formula reduces to the expression previously derived by den Otter and Briels. If simulations are carried out without constraining the coordinates of interest, the formula leads to a new method for calculating the free energy changes along these coordinates. This method is tested in two examples - rotation around the C-C bond of 1,2-dichloroethane immersed in water and transfer of fluoromethane across the water-hexane interface. The calculated free energies are compared with those obtained by two commonly used methods. One of them relies on determining the probability density function of finding the system at different values of the selected coordinate and the other requires calculating the average force at discrete locations along this coordinate in a series of constrained simulations. The free energies calculated by these three methods are in excellent agreement. The relative advantages of each method are discussed.

  14. Calculation of the Ionization Potentials and Electron Affinities for Atoms

    NASA Astrophysics Data System (ADS)

    Chen, Jiqiang; Krieger, J. B.; Iafrate, G. J.; Savin, A.

    1998-03-01

    The method employing the self-interaction-corrected correlation energy functional obtained from the homogeneous electron gas with a gap is extended to atoms and ions with non-zero spin polarization. As in the case for atoms and ions with ζ=3D0, the error in the calculated Ec is significantly smaller than in the LSD approximation with zero gap for atoms and ions with Z<=18. Comparison of the resulting ionization potentials and electron affinities with experimental values will also be presented. Finally, we will discuss the possibility of obtaining saturation for Ec for the He, Li, N, O, F and Ne isoelectronic series, but a divergent Ec for the Be, B and C isoelectronic series, in the large Z limit.

  15. Accurate ionization potential of semiconductors from efficient density functional calculations

    NASA Astrophysics Data System (ADS)

    Ye, Lin-Hui

    2016-07-01

    Despite its huge successes in total-energy-related applications, the Kohn-Sham scheme of density functional theory cannot get reliable single-particle excitation energies for solids. In particular, it has not been able to calculate the ionization potential (IP), one of the most important material parameters, for semiconductors. We illustrate that an approximate exact-exchange optimized effective potential (EXX-OEP), the Becke-Johnson exchange, can be used to largely solve this long-standing problem. For a group of 17 semiconductors, we have obtained the IPs to an accuracy similar to that of the much more sophisticated G W approximation (GWA), with the computational cost of only local-density approximation/generalized gradient approximation. The EXX-OEP, therefore, is likely as useful for solids as for finite systems. For solid surfaces, the asymptotic behavior of the vx c has effects similar to those of finite systems which, when neglected, typically cause the semiconductor IPs to be underestimated. This may partially explain why standard GWA systematically underestimates the IPs and why using the same GWA procedures has not been able to get an accurate IP and band gap at the same time.

  16. Protein thermostability calculations using alchemical free energy simulations.

    PubMed

    Seeliger, Daniel; de Groot, Bert L

    2010-05-19

    Thermal stability of proteins is crucial for both biotechnological and therapeutic applications. Rational protein engineering therefore frequently aims at increasing thermal stability by introducing stabilizing mutations. The accurate prediction of the thermodynamic consequences caused by mutations, however, is highly challenging as thermal stability changes are caused by alterations in the free energy of folding. Growing computational power, however, increasingly allows us to use alchemical free energy simulations, such as free energy perturbation or thermodynamic integration, to calculate free energy differences with relatively high accuracy. In this article, we present an automated protocol for setting up alchemical free energy calculations for mutations of naturally occurring amino acids (except for proline) that allows an unprecedented, automated screening of large mutant libraries. To validate the developed protocol, we calculated thermodynamic stability differences for 109 mutations in the microbial Ribonuclease Barnase. The obtained quantitative agreement with experimental data illustrates the potential of the approach in protein engineering and design. PMID:20483340

  17. Monte Carlo algorithm for free energy calculation.

    PubMed

    Bi, Sheng; Tong, Ning-Hua

    2015-07-01

    We propose a Monte Carlo algorithm for the free energy calculation based on configuration space sampling. An upward or downward temperature scan can be used to produce F(T). We implement this algorithm for the Ising model on a square lattice and triangular lattice. Comparison with the exact free energy shows an excellent agreement. We analyze the properties of this algorithm and compare it with the Wang-Landau algorithm, which samples in energy space. This method is applicable to general classical statistical models. The possibility of extending it to quantum systems is discussed.

  18. Alaska's renewable energy potential.

    SciTech Connect

    Not Available

    2009-02-01

    This paper delivers a brief survey of renewable energy technologies applicable to Alaska's climate, latitude, geography, and geology. We first identify Alaska's natural renewable energy resources and which renewable energy technologies would be most productive. e survey the current state of renewable energy technologies and research efforts within the U.S. and, where appropriate, internationally. We also present information on the current state of Alaska's renewable energy assets, incentives, and commercial enterprises. Finally, we escribe places where research efforts at Sandia National Laboratories could assist the state of Alaska with its renewable energy technology investment efforts.

  19. High-level ab initio calculations for the four low-lying families of minima of (H2O)(20): 1. Estimates of MP2/CBS binding energies and comparison with empirical potentials

    SciTech Connect

    Fanourgakis, Georgios S.; Apra, Edoardo; Xantheas, Sotiris S.

    2004-08-08

    We report estimates of complete basis set (CBS) limits at the second-order Møller-Plesset perturbation level of theory (MP2) for the binding energies of the lowest lying isomers within each of the four major families of minima of (H2O)20. These were obtained by performing MP2 calculations with the family of correlation-consistent basis sets up to quadruple zeta quality, augmented with additional diffuse functions (aug-cc-pVnZ, n=D, T, Q). The MP2/CBS estimates are: -200.1 kcal/mol (dodecahedron, 30 hydrogen bonds), -212.6 kcal/mol (fused cubes, 36 hydrogen bonds), -215.0 (face-sharing pentagonal prisms, 35 hydrogen bonds) and –217.9 kcal/mol (edge-sharing pentagonal prisms, 34 hydrogen bonds). The energetic ordering of the various (H2O)20 isomers does not follow monotonically the number of hydrogen bonds as in the case of smaller clusters such as the different isomers of the water hexamer. The dodecahedron lies ca. 18 kcal/mol higher in energy than the most stable edge-sharing pentagonal prism isomer. The TIP4P, ASP-W4, TTM2-R, AMOEBA and TTM2-F empirical potentials also predict the energetic stabilization of the edge-sharing pentagonal prisms with respect to the dodecahedron, albeit they universally underestimate the cluster binding energies with respect to the MP2/CBS result. Among them, the TTM2-F potential was found to predict the absolute cluster binding energies to within < 1% from the corresponding MP2/CBS values, whereas the error for the rest of the potentials considered in this study ranges from 3-5%.

  20. Free energy calculations of gramicidin dimer dissociation.

    PubMed

    Wanasundara, Surajith N; Krishnamurthy, Vikram; Chung, Shin-Ho

    2011-11-24

    Molecular dynamics simulations, combined with umbrella sampling, is used to study how gramicidin A (gA) dimers dissociate in the lipid bilayer. The potential of mean force and intermolecular potential energy are computed as functions of the distance between center of masses of the two gA monomers in two directions of separation: parallel to the bilayer surface and parallel to the membrane normal. Results from this study show that the dissociation of gA dimers occurs via lateral displacement of gA monomers followed by tilting of dimers with respect to the lipid bilayer normal. It is found that the dissociation energy of gA dimers in the dimyristoylphosphatidylcholine bilayer is 14 kcal mol(-1) (~22 kT), which is approximately equal to the energy of breaking six intermolecular hydrogen bonds that stabilize the gA channel dimer.

  1. On the calculation of classical vibrational energy exchange

    NASA Astrophysics Data System (ADS)

    Gibbons, John P.; Stettler, John D.

    1982-07-01

    A three-dimensional, Monte Carlo classical model for the calculation of vibrational energy relaxation and transfer rates for both diatomic—monatomic and diatomic—diatomic systems was developed, analyzed and implemented. Mediation by internal angular momentum changes was demonstrated to be important in these energy transfer processes. This mechanism was incorporated into the model in order to achieve statistically significant results within reasonable computer running times. This made possible the extension of the model calculations to much lower temperatures than had been previously investigated. This calculational procedure was applied to Ar—O 2, to He—O 2 and to the near resonant CO—N 2 process at several temperatures between room temperature and 4000 K with the use of exponential repulsive intermolecular potential. Three different sets of potential parameters obtained from three independent sources were used. The results were compared to experiment.

  2. Rate constant calculations of the GeH4 + OH/OD → GeH3 + H2O/HOD reactions using an ab initio based full-dimensional potential energy surface.

    PubMed

    Espinosa-Garcia, J; Rangel, C; Corchado, J C

    2016-06-22

    We report an analytical full-dimensional potential energy surface for the GeH4 + OH → GeH3 + H2O reaction based on ab initio calculations. It is a practically barrierless reaction with very high exothermicity and the presence of intermediate complexes in the entrance and exit channels, reproducing the experimental evidence. Using this surface, thermal rate constants for the GeH4 + OH/OD isotopic reactions were calculated using two approaches: variational transition state theory (VTST) and quasi-classical trajectory (QCT) calculations, in the temperature range 200-1000 K, and results were compared with the only experimental data at 298 K. Both methods showed similar values over the whole temperature range, with differences less than 30%; and the experimental data was reproduced at 298 K, with negative temperature dependence below 300 K, which is associated with the presence of an intermediate complex in the entrance channel. However, while the QCT approach reproduced the experimental kinetic isotope effect, the VTST approach underestimated it. We suggest that this difference is associated with the harmonic approximation used in the treatment of vibrational frequencies.

  3. Ab initio calculations on potential energy curves and radiative lifetimes for the band systems A(2)Π-X(2)Σ(+) of magnesium monohalides MgX (X=F, Cl, Br, I).

    PubMed

    Wu, Dong-lan; Tan, Bin; Qin, Jiu-ying; Wan, Hui-jun; Xie, An-dong; Yan, Bing; Ding, Da-jun

    2015-11-01

    Ab initio calculations on potential energy curves (PECs), spectroscopic constants, transition dipole moments, radiative transition probabilities and lifetimes for the ground state (X(2)Σ(+)) and the first excited state (A(2)Π) of MgX (X=F, Cl, Br, I) molecules are determined by high-level internally contracted multi-reference configuration interaction (ic-MRCI) method. In order to improve the calculation, the Davidson modification (+Q) and scalar relativistic correction are included. The present results show that most of spectroscopic constants are in accordance with the measurements, the equilibrium internuclear distance Re increases while the other spectroscopic constants reduce along with the increasing of the atomic number of the halogen from F to I. Diagonal vibrational transitions are found to be dominant for the A(2)Π→X(2)Σ(+) system of MgX molecules. The corresponding radiative lifetimes of ν'=0 are computed to be 7.24, 9.98, 18.94 and 22.72 ns for MgF, MgCl, MgBr, and MgI, respectively. The calculated result of MgF molecule is in good agreement with the recent theoretical result of 7.16 ns, with a small relative error percent of 1.11%.

  4. Rate constant calculations of the GeH4 + OH/OD → GeH3 + H2O/HOD reactions using an ab initio based full-dimensional potential energy surface.

    PubMed

    Espinosa-Garcia, J; Rangel, C; Corchado, J C

    2016-06-22

    We report an analytical full-dimensional potential energy surface for the GeH4 + OH → GeH3 + H2O reaction based on ab initio calculations. It is a practically barrierless reaction with very high exothermicity and the presence of intermediate complexes in the entrance and exit channels, reproducing the experimental evidence. Using this surface, thermal rate constants for the GeH4 + OH/OD isotopic reactions were calculated using two approaches: variational transition state theory (VTST) and quasi-classical trajectory (QCT) calculations, in the temperature range 200-1000 K, and results were compared with the only experimental data at 298 K. Both methods showed similar values over the whole temperature range, with differences less than 30%; and the experimental data was reproduced at 298 K, with negative temperature dependence below 300 K, which is associated with the presence of an intermediate complex in the entrance channel. However, while the QCT approach reproduced the experimental kinetic isotope effect, the VTST approach underestimated it. We suggest that this difference is associated with the harmonic approximation used in the treatment of vibrational frequencies. PMID:27292879

  5. Bond-Energy and Surface-Energy Calculations in Metals

    ERIC Educational Resources Information Center

    Eberhart, James G.; Horner, Steve

    2010-01-01

    A simple technique appropriate for introductory materials science courses is outlined for the calculation of bond energies in metals from lattice energies. The approach is applied to body-centered cubic (bcc), face-centered cubic (fcc), and hexagonal-closest-packed (hcp) metals. The strength of these bonds is tabulated for a variety metals and is…

  6. The theoretical shape of sucrose crystals from energy calculations

    NASA Astrophysics Data System (ADS)

    Saska, Michael; Myerson, Allan S.

    1983-05-01

    The surface energies of individual crystallographic faces of crystalline sucrose were calculated using two forms of the 6-exp (Buckingham) potential. Hydrogen bond energies were calculated as a sum of O-H, O…H and O…O interactions where the Lippincott-Schroeder short-range potential was used for O-H and O…H pairs and the 6-exp potential for the non-bonded O…O interactions. Assuming that the surface energy equals half of the cohesive energy of the crystal, the attachment and surface energies of most of the faces found on as sucrose crystal were calculated. A computer program was written to draw the theoretical shape of crystals given the positions (central distances) of its faces. The resulting sucrose shapes are elongated along the c-axis. It is argued that the c-axis elongated habit is an intrinsic shape for vapor grown sucrose crystals (if realizable) and it is suggested that the usual shapes of solution grown sucrose crystals can be explained in terms of solvent (water) adsorption.

  7. Potential Energy Curves of Hydrogen Fluoride

    NASA Technical Reports Server (NTRS)

    Fallon, Robert J.; Vanderslice, Joseph T.; Mason, Edward A.

    1960-01-01

    Potential energy curves for the X(sup 1)sigma+ and V(sup 1)sigma+ states of HF and DF have been calculated by the Rydberg-Klein-Rees method. The results calculated from the different sets of data for HF and DF are found to be in very good agreement. The theoretical results of Karo are compared to the experimental results obtained here.

  8. Chemical potential calculations in dense liquids using metadynamics

    NASA Astrophysics Data System (ADS)

    Perego, C.; Giberti, F.; Parrinello, M.

    2016-07-01

    The calculation of chemical potential has traditionally been a challenge in atomistic simulations. One of the most used approaches is Widom's insertion method in which the chemical potential is calculated by periodically attempting to insert an extra particle in the system. In dense systems this method fails since the insertion probability is very low. In this paper we show that in a homogeneous fluid the insertion probability can be increased using metadynamics. We test our method on a supercooled high density binary Lennard-Jones fluid. We find that we can obtain efficiently converged results even when Widom's method fails.

  9. Computer programs for calculating potential flow in propulsion system inlets

    NASA Technical Reports Server (NTRS)

    Stockman, N. O.; Button, S. L.

    1973-01-01

    In the course of designing inlets, particularly for VTOL and STOL propulsion systems, a calculational procedure utilizing three computer programs evolved. The chief program is the Douglas axisymmetric potential flow program called EOD which calculates the incompressible potential flow about arbitrary axisymmetric bodies. The other two programs, original with Lewis, are called SCIRCL AND COMBYN. Program SCIRCL generates input for EOD from various specified analytic shapes for the inlet components. Program COMBYN takes basic solutions output by EOD and combines them into solutions of interest, and applies a compressibility correction.

  10. Lead Optimization Mapper: Automating free energy calculations for lead optimization

    PubMed Central

    Liu, Shuai; Wu, Yujie; Lin, Teng; Abel, Robert; Redmann, Jonathan P.; Summa, Christopher M.; Jaber, Vivian R.; Lim, Nathan M.; Mobley, David L.

    2013-01-01

    Alchemical free energy calculations hold increasing promise as an aid to drug discovery efforts. However, applications of these techniques in discovery projects have been relatively few, partly because of the difficulty of planning and setting up calculations. Here, we introduce Lead Optimization Mapper, LOMAP, an automated algorithm to plan efficient relative free energy calculations between potential ligands within a substantial library of perhaps hundreds of compounds. In this approach, ligands are first grouped by structural similarity primarily based on the size of a (loosely defined) maximal common substructure, and then calculations are planned within and between sets of structurally related compounds. An emphasis is placed on ensuring that relative free energies can be obtained between any pair of compounds without combining the results of too many different relative free energy calculations (to avoid accumulation of error) and by providing some redundancy to allow for the possibility of error and consistency checking and provide some insight into when results can be expected to be unreliable. The algorithm is discussed in detail and a Python implementation, based on both Schrödinger's and OpenEye's APIs, has been made available freely under the BSD license. PMID:24072356

  11. Dirac Calculations for Proton Inelastic Scattering at Intermediate Energies

    NASA Astrophysics Data System (ADS)

    El-Nohy, N. A.; El-Hammamy, M. N.; Aly, N. E.; Abdel-Moneim, A. M.; Hamza, A. F.

    2016-09-01

    Relativistic proton inelastic scattering from different targets (16O, 24Mg, 28Si, 40Ca, 54Fe, 58Ni, 90Zr, 154Sm, 176Yb, and 208Pb) at intermediate energies is analyzed in the framework of phenomenological optical potentials based on the Dirac formalism. Parameters of the Dirac phenomenological potential with Woods Saxon (WS) shape are obtained. The first order vibrational collective model with one phonon is used to calculate the transition optical potentials to the first low-lying excited state (2+) of the investigated target nuclei. Also, the variation of deformation length (δ) with energy and mass number is studied. It is noticed that the deformation length increases slightly with energy at intermediate range.

  12. Calculation of interaction-induced spectra using complex absorbing potentials

    SciTech Connect

    Gustafsson, Magnus; Antipov, Sergey V.

    2010-10-29

    A complex absorbing potential method is implemented for calculation of collision-induced spectra. The scheme provides a way to avoid the integration of the Schroedinger equation to very large separations of the collisional pair. The method is tested by reproducing a previously computed absorption spectrum for H-He at two different temperatures.

  13. LHC Physics Potential versus Energy

    SciTech Connect

    Quigg, Chris; /Fermilab

    2009-08-01

    Parton luminosities are convenient for estimating how the physics potential of Large Hadron Collider experiments depends on the energy of the proton beams. I present parton luminosities, ratios of parton luminosities, and contours of fixed parton luminosity for gg, u{bar d}, and qq interactions over the energy range relevant to the Large Hadron Collider, along with example analyses for specific processes.

  14. Potential energy function for the hydroperoxyl radical

    SciTech Connect

    Lemon, W.J.; Hase, W.L.

    1987-03-12

    A switching function formalism is used to derive an analytic potential energy surface for the O + OH in equilibrium HO/sub 2/ in equilibrium H + O/sub 2/ reactive system. Both experimental and ab initio data are used to derive parameters for the potential energy surface. Trajectory calculations for highly excited HO/sub 2/ are performed on this surface. From these trajectories quasi-periodic eigentrajectories are found for vibrational levels near the HO/sub 2/ dissociation threshold with small amounts of quanta in the OH stretch mode and large amounts of quanta in the OO stretch mode.

  15. Off disk-center potential field calculations using vector magnetograms

    NASA Technical Reports Server (NTRS)

    Venkatakrishnan, P.; Gary, G. Allen

    1989-01-01

    A potential field calculation for off disk-center vector magnetograms that uses all the three components of the measured field is investigated. There is neither any need for interpolation of grid points between the image plane and the heliographic plane nor for an extension or a truncation to a heliographic rectangle. Hence, the method provides the maximum information content from the photospheric field as well as the most consistent potential field independent of the viewing angle. The introduction of polarimetric noise produces a less tolerant extrapolation procedure than using the line-of-sight extrapolation, but the resultant standard deviation is still small enough for the practical utility of this method.

  16. Eight-dimensional quantum reaction rate calculations for the H+CH{sub 4} and H{sub 2}+CH{sub 3} reactions on recent potential energy surfaces

    SciTech Connect

    Zhou, Yong; Zhang, Dong H.

    2014-11-21

    Eight-dimensional (8D) transition-state wave packet simulations have been performed on two latest potential energy surfaces (PES), the Zhou-Fu-Wang-Collins-Zhang (ZFWCZ) PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)] and the Xu-Chen-Zhang (XCZ)-neural networks (NN) PES [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. Reaction rate constants for both the H+CH{sub 4} reaction and the H{sub 2}+CH{sub 3} reaction are calculated. Simulations of the H+CH{sub 4} reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable high accuracy for low temperatures while leads to slightly lower results for high temperatures, in line with the distribution of interpolation error associated with the ZFWCZ PES. The 8D H+CH{sub 4} rate constants derived on the ZFWCZ PES compare well with full-dimensional 12D results based on the equivalent m-ZFWCZ PES, with a maximum relative difference of no more than 20%. Additionally, very good agreement is shown by comparing the 8D XCZ-NN rate constants with the 12D results obtained on the ZFWCZ-WM PES, after considering the difference in static barrier height between these two PESs. The reaction rate constants calculated for the H{sub 2}+CH{sub 3} reaction are found to be in good consistency with experimental observations.

  17. Reaction Dynamics of O((3)P) + Propyne: II. Primary Products, Branching Ratios, and Role of Intersystem Crossing from Ab Initio Coupled Triplet/Singlet Potential Energy Surfaces and Statistical Calculations.

    PubMed

    Gimondi, Ilaria; Cavallotti, Carlo; Vanuzzo, Gianmarco; Balucani, Nadia; Casavecchia, Piergiorgio

    2016-07-14

    The mechanism of the O((3)P) + CH3CCH reaction was investigated using a combined experimental/theoretical approach. Experimentally the reaction dynamics was studied using crossed molecular beams (CMB) with mass-spectrometric detection and time-of-flight analysis at 9.2 kcal/mol collision energy. Theoretically master equation (ME) simulations were performed on a potential energy surface (PES) determined using high-level ab initio electronic structure calculations. In this paper (II) the theoretical results are described and compared with experiments, while in paper (I) are reported and discussed the results of the experimental study. The PES was investigated by determining structures and vibrational frequencies of wells and transition states at the CASPT2/aug-cc-pVTZ level using a minimal active space. Energies were then determined at the CASPT2 level increasing systematically the active space and at the CCSD(T) level extrapolating to the complete basis set limit. Two separate portions of the triplet PES were investigated, as O((3)P) can add either on the terminal or the central carbon of the unsaturated propyne bond. Minimum energy crossing points (MECPs) between the triplet and singlet PESs were searched at the CASPT2 level. The calculated spin-orbit coupling constants between the T1 and S0 electronic surfaces were ∼25 cm(-1) for both PESs. The portions of the singlet PES that can be accessed from the MECPs were investigated at the same level of theory. The system reactivity was predicted integrating stochastically the one-dimensional ME using Rice-Ramsperger-Kassel-Marcus theory to determine rate constants on the full T1/S0 PESs, accounting explicitly for intersystem crossing (ISC) using the Landau-Zener model. The computational results are compared both with the branching ratios (BRs) determined experimentally in the companion paper (I) and with those estimated in a recent kinetic study at 298 K. The ME results allow to interpret the main system reactivity: CH

  18. Reaction Dynamics of O((3)P) + Propyne: II. Primary Products, Branching Ratios, and Role of Intersystem Crossing from Ab Initio Coupled Triplet/Singlet Potential Energy Surfaces and Statistical Calculations.

    PubMed

    Gimondi, Ilaria; Cavallotti, Carlo; Vanuzzo, Gianmarco; Balucani, Nadia; Casavecchia, Piergiorgio

    2016-07-14

    The mechanism of the O((3)P) + CH3CCH reaction was investigated using a combined experimental/theoretical approach. Experimentally the reaction dynamics was studied using crossed molecular beams (CMB) with mass-spectrometric detection and time-of-flight analysis at 9.2 kcal/mol collision energy. Theoretically master equation (ME) simulations were performed on a potential energy surface (PES) determined using high-level ab initio electronic structure calculations. In this paper (II) the theoretical results are described and compared with experiments, while in paper (I) are reported and discussed the results of the experimental study. The PES was investigated by determining structures and vibrational frequencies of wells and transition states at the CASPT2/aug-cc-pVTZ level using a minimal active space. Energies were then determined at the CASPT2 level increasing systematically the active space and at the CCSD(T) level extrapolating to the complete basis set limit. Two separate portions of the triplet PES were investigated, as O((3)P) can add either on the terminal or the central carbon of the unsaturated propyne bond. Minimum energy crossing points (MECPs) between the triplet and singlet PESs were searched at the CASPT2 level. The calculated spin-orbit coupling constants between the T1 and S0 electronic surfaces were ∼25 cm(-1) for both PESs. The portions of the singlet PES that can be accessed from the MECPs were investigated at the same level of theory. The system reactivity was predicted integrating stochastically the one-dimensional ME using Rice-Ramsperger-Kassel-Marcus theory to determine rate constants on the full T1/S0 PESs, accounting explicitly for intersystem crossing (ISC) using the Landau-Zener model. The computational results are compared both with the branching ratios (BRs) determined experimentally in the companion paper (I) and with those estimated in a recent kinetic study at 298 K. The ME results allow to interpret the main system reactivity: CH

  19. Relativity, potential energy, and mass

    NASA Astrophysics Data System (ADS)

    Hecht, Eugene

    2016-11-01

    This paper is an exploration of the concept of energy, illuminated by the transformative insights of the special theory of relativity. Focusing on potential energy (PE), it will be shown that PE as presently defined is in conflict with the tenets of special relativity. Even though PE remains an indispensable theoretical device its actual physicality is questionable. Moreover its ontological status is quite different from that of both kinetic energy and mass, a significant point that is not widely appreciated. We will establish that PE is a theoretical concept as opposed to an empirical one; it is a descriptor of mass-energy without a detectable physical presence of its own. PE is a measure of energy stored, it is not the energy stored.

  20. Theoretical studies of potential energy surfaces.

    SciTech Connect

    Harding, L. B.

    2006-01-01

    The goal of this program is to calculate accurate potential energy surfaces for both reactive and nonreactive systems. To do this the electronic Schroedinger equation must be solved. Our approach starts with multiconfiguration self-consistent field (MCSCF) reference wave functions. These reference wavefunctions are designed to be sufficiently flexible to accurately describe changes in electronic structure over a broad range of geometries. Dynamical electron correlation effects are included via multireference, singles and doubles configuration interaction (MRCI) calculations. With this approach, we are able to provide chemically useful predictions of the energetics for many systems. A second aspect of this program is the development of techniques to fit multi-dimensional potential surfaces to convenient, global, analytic functions that can then be used in dynamics calculations.

  1. Theoretical studies of potential energy surfaces

    SciTech Connect

    Harding, L.B.

    1993-12-01

    The goal of this program is to calculate accurate potential energy surfaces (PES) for both reactive and nonreactive systems. To do this the electronic Schrodinger equation must be solved. Our approach to this problem starts with multiconfiguration self-consistent field (MCSCF) reference wavefunctions. These reference wavefunctions are designed to be sufficiently flexible to accurately describe changes in electronic structure over a broad range of geometries. Electron correlation effects are included via multireference, singles and doubles configuration interaction (MRSDCI) calculations. With this approach, the authors are able to provide useful predictions of the energetics for a broad range of systems.

  2. Calculations in support of a potential definition of large release

    SciTech Connect

    Hanson, A.L.; Davis, R.E.; Mubayi, V.

    1994-05-01

    The Nuclear Regulatory Commission has stated a hierarchy of safety goals with the qualitative safety goals as Level I of the hierarchy, backed up by the quantitative health objectives as Level II and the large release guideline as Level III. The large release guideline has been stated in qualitative terms as a magnitude of release of the core inventory whose frequency should not exceed 10{sup -6} per reactor year. However, the Commission did not provide a quantitative specification of a large release. This report describes various specifications of a large release and focuses, in particular, on an examination of releases which have a potential to lead to one prompt fatality in the mean. The basic information required to set up the calculations was derived from the simplified source terms which were obtained from approximations of the NUREG-1150 source terms. Since the calculation of consequences is affected by a large number of assumptions, a generic site with a (conservatively determined) population density and meteorology was specified. At this site, various emergency responses (including no response) were assumed based on information derived from earlier studies. For each of the emergency response assumptions, a set of calculations were performed with the simplified source terms; these included adjustments to the source terms, such as the timing of the release, the core inventory, and the release fractions of different radionuclides, to arrive at a result of one mean prompt fatality in each case. Each of the source terms, so defined, has the potential to be a candidate for a large release. The calculations show that there are many possible candidate source terms for a large release depending on the characteristics which are felt to be important.

  3. Exchange-only optimized effective potential calculation of excited state spectra for He and Be atoms.

    SciTech Connect

    Desjarlais, Michael Paul; Muller, Richard Partain

    2006-02-01

    The optimized effective potential (OEP) method allows orbital-dependent functionals to be used in density functional theory (DFT), which, in particular, allows exact exchange formulations of the exchange energy to be used in DFT calculations. Because the exact exchange is inherently self-interaction correcting, the resulting OEP calculations have been found to yield superior band-gaps for condensed-phase systems. Here we apply these methods to the isolated atoms He and Be, and compare to high quality experiments and calculations to demonstrate that the orbital energies accurately reproduce the excited state spectrum for these species. These results suggest that coupling the exchange-only OEP calculations with proper (orbital-dependent or other) correlation functions might allow quantitative accuracy from DFT calculations.

  4. The potential of renewable energy

    NASA Astrophysics Data System (ADS)

    1990-03-01

    On June 27 and 28, 1989, the U.S. DOE national labs were convened to discuss plans for the development of a National Energy Strategy (NES) and, in particular, the analytic needs in support of NES that could be addressed by the labs. As a result of that meeting, interlabor teams were formed to produce analytic white papers on key topics, and a lead lab was designated for each core lab team. The broad-ranging renewables assignment is summarized by the following issue statement from the Office of Policy, Planning and Analysis: to what extent can renewable energy technologies contribute to diversifying sources of energy supply; What are the major barriers to greater renewable energy use and what is the potential timing of widespread commercialization for various categories of applications. The results are presented of the intensive activity initiated by the June 1989 meeting to produce a white paper on renewable energy.

  5. Improved initial guess for minimum energy path calculations.

    PubMed

    Smidstrup, Søren; Pedersen, Andreas; Stokbro, Kurt; Jónsson, Hannes

    2014-06-01

    A method is presented for generating a good initial guess of a transition path between given initial and final states of a system without evaluation of the energy. An objective function surface is constructed using an interpolation of pairwise distances at each discretization point along the path and the nudged elastic band method then used to find an optimal path on this image dependent pair potential (IDPP) surface. This provides an initial path for the more computationally intensive calculations of a minimum energy path on an energy surface obtained, for example, by ab initio or density functional theory. The optimal path on the IDPP surface is significantly closer to a minimum energy path than a linear interpolation of the Cartesian coordinates and, therefore, reduces the number of iterations needed to reach convergence and averts divergence in the electronic structure calculations when atoms are brought too close to each other in the initial path. The method is illustrated with three examples: (1) rotation of a methyl group in an ethane molecule, (2) an exchange of atoms in an island on a crystal surface, and (3) an exchange of two Si-atoms in amorphous silicon. In all three cases, the computational effort in finding the minimum energy path with DFT was reduced by a factor ranging from 50% to an order of magnitude by using an IDPP path as the initial path. The time required for parallel computations was reduced even more because of load imbalance when linear interpolation of Cartesian coordinates was used.

  6. Improved initial guess for minimum energy path calculations

    SciTech Connect

    Smidstrup, Søren; Pedersen, Andreas; Stokbro, Kurt

    2014-06-07

    A method is presented for generating a good initial guess of a transition path between given initial and final states of a system without evaluation of the energy. An objective function surface is constructed using an interpolation of pairwise distances at each discretization point along the path and the nudged elastic band method then used to find an optimal path on this image dependent pair potential (IDPP) surface. This provides an initial path for the more computationally intensive calculations of a minimum energy path on an energy surface obtained, for example, by ab initio or density functional theory. The optimal path on the IDPP surface is significantly closer to a minimum energy path than a linear interpolation of the Cartesian coordinates and, therefore, reduces the number of iterations needed to reach convergence and averts divergence in the electronic structure calculations when atoms are brought too close to each other in the initial path. The method is illustrated with three examples: (1) rotation of a methyl group in an ethane molecule, (2) an exchange of atoms in an island on a crystal surface, and (3) an exchange of two Si-atoms in amorphous silicon. In all three cases, the computational effort in finding the minimum energy path with DFT was reduced by a factor ranging from 50% to an order of magnitude by using an IDPP path as the initial path. The time required for parallel computations was reduced even more because of load imbalance when linear interpolation of Cartesian coordinates was used.

  7. Energies of Screened Coulomb Potentials.

    ERIC Educational Resources Information Center

    Lai, C. S.

    1979-01-01

    This article shows that, by applying the Hellman-Feynman theorem alone to screened Coulomb potentials, the first four coefficients in the energy series in powers of the perturbation parameter can be obtained from the unperturbed Coulomb system. (Author/HM)

  8. Non-Equilibrium Properties from Equilibrium Free Energy Calculations

    NASA Technical Reports Server (NTRS)

    Pohorille, Andrew; Wilson, Michael A.

    2012-01-01

    Calculating free energy in computer simulations is of central importance in statistical mechanics of condensed media and its applications to chemistry and biology not only because it is the most comprehensive and informative quantity that characterizes the eqUilibrium state, but also because it often provides an efficient route to access dynamic and kinetic properties of a system. Most of applications of equilibrium free energy calculations to non-equilibrium processes rely on a description in which a molecule or an ion diffuses in the potential of mean force. In general case this description is a simplification, but it might be satisfactorily accurate in many instances of practical interest. This hypothesis has been tested in the example of the electrodiffusion equation . Conductance of model ion channels has been calculated directly through counting the number of ion crossing events observed during long molecular dynamics simulations and has been compared with the conductance obtained from solving the generalized Nernst-Plank equation. It has been shown that under relatively modest conditions the agreement between these two approaches is excellent, thus demonstrating the assumptions underlying the diffusion equation are fulfilled. Under these conditions the electrodiffusion equation provides an efficient approach to calculating the full voltage-current dependence routinely measured in electrophysiological experiments.

  9. Comparison of Electron Elastic-Scattering Cross Sections Calculated from Two Commonly Used Atomic Potentials

    NASA Astrophysics Data System (ADS)

    Jablonski, A.; Salvat, F.; Powell, C. J.

    2004-06-01

    We have analyzed differential cross sections (DCSs) for the elastic scattering of electrons by neutral atoms that have been derived from two commonly used atomic potentials: the Thomas-Fermi-Dirac (TFD) potential and the Dirac-Hartree-Fock (DHF) potential. DCSs from the latter potential are believed to be more accurate. We compared DCSs for six atoms (H, Al, Ni, Ag, Au, and Cm) at four energies (100, 500, 1000, and 10 000 eV) from two databases issued by the National Institute of Standards and Technology in which DCSs had been obtained from the TFD and DHF potentials. While the DCSs from the two potentials had similar shapes and magnitudes, there can be pronounced deviations (up to 70%) for small scattering angles for Al, Ag, Au, and Cm. In addition, there were differences of up to 400% at scattering angles for which there were deep minima in the DCSs; at other angles, the differences were typically less than 20%. The DCS differences decreased with increasing electron energy. DCSs calculated from the two potentials were compared with measured DCSs for six atoms (He, Ne, Ar, Kr, Xe, and Hg) at energies between 50 eV and 3 keV. For Ar, the atom for which experimental data are available over the largest energy range there is good agreement between the measured DCSs and those calculated from the TFD and DHF potentials at 2 and 3 keV, but the experimental DCSs agree better with the DCSs from the DHF potential at lower energies. A similar trend is found for the other atoms. At energies less than about 1 keV, there are increasing differences between the measured DCSs and the DCSs calculated from the DHF potential. These differences were attributed to the neglect of absorption and polarizability effects in the calculations. We compare transport cross sections for H, Al, Ni, Ag, Au, and Cm obtained from the DCSs for each potential. For energies between 200 eV and 1 keV, the largest differences are about 20% (for H, Au, and Cm); at higher energies, the differences are

  10. California Industrial Energy Efficiency Potential

    SciTech Connect

    Coito, Fred; Worrell, Ernst; Price, Lynn; Masanet, Eric; RafaelFriedmann; Rufo, Mike

    2005-06-01

    This paper presents an overview of the modeling approach andhighlights key findings of a California industrial energy efficiencypotential study. In addition to providing estimates of technical andeconomic potential, the study examines achievable program potential undervarious program-funding scenarios. The focus is on electricity andnatural gas savings for manufacturing in the service territories ofCalifornia's investor-owned utilities (IOUs). The assessment is conductedby industry type and by end use. Both crosscutting technologies andindustry-specific process measures are examined. Measure penetration intothe marketplace is modeled as a function of customer awareness, measurecost effectiveness, and perceived market barriers. Data for the studycomes from a variety of sources, including: utility billing records, theEnergy Information Association (EIA) Manufacturing Energy ConsumptionSurvey (MECS), state-sponsored avoided cost studies, energy efficiencyprogram filings, and technology savings and cost data developed throughLawrence Berkeley National Laboratory (LBNL). The study identifies 1,706GWh and 47 Mth (million therms) per year of achievable potential over thenext twelve years under recent levels of program expenditures, accountingfor 5.2 percent of industrial electricity consumption and 1.3 percent ofindustrial natural gas consumption. These estimates grow to 2,748 GWh and192 Mth per year if all cost-effective and achievable opportunities arepursued. Key industrial electricity end uses, in terms of energy savingspotential, include compressed air and pumping systems that combine toaccount for about half of the total achievable potential estimates. Fornatural gas, savings are concentrated in the boiler and process heatingend uses, accounting for over 99 percent to total achievablepotential.

  11. Bonn potential and shell-model calculations for N=126 isotones

    SciTech Connect

    Coraggio, L.; Covello, A.; Gargano, A.; Itaco, N.; Kuo, T. T. S.

    1999-12-01

    We have performed shell-model calculations for the N=126 isotones {sup 210}Po, {sup 211}At, and {sup 212}Rn using a realistic effective interaction derived from the Bonn-A nucleon-nucleon potential by means of a G-matrix folded-diagram method. The calculated binding energies, energy spectra, and electromagnetic properties show remarkably good agreement with the experimental data. The results of this paper complement those of our previous study on neutron hole Pb isotopes, confirming that realistic effective interactions are now able to reproduce with quantitative accuracy the spectroscopic properties of complex nuclei. (c) 1999 The American Physical Society.

  12. Potential energy savings from aquifer thermal energy storage

    SciTech Connect

    Anderson, M.R.; Weijo, R.O.

    1988-07-01

    Pacific Northwest Laboratory researchers developed an aggregate-level model to estimate the short- and long-term potential energy savings from using aquifer thermal storage (ATES) in the United States. The objectives of this effort were to (1) develop a basis from which to recommend whether heat or chill ATES should receive future research focus and (2) determine which market sector (residential, commercial, or industrial) offers the largest potential energy savings from ATES. Information was collected on the proportion of US land area suitable for ATES applications. The economic feasibility of ATES applications was then evaluated. The potential energy savings from ATES applications was calculated. Characteristic energy use in the residential, commercial, and industrial sectors was examined, as was the relationship between waste heat production and consumption by industrial end-users. These analyses provided the basis for two main conclusions: heat ATES applications offer higher potential for energy savings than do chill ATES applications; and the industrial sector can achieve the highest potential energy savings for the large consumption markets. Based on these findings, it is recommended that future ATES research and development efforts be directed toward heat ATES applications in the industrial sector. 11 refs., 6 figs., 9 tabs.

  13. Computed potential energy surfaces for chemical reactions

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    1988-01-01

    The minimum energy path for the addition of a hydrogen atom to N2 is characterized in CASSCF/CCI calculations using the (4s3p2d1f/3s2p1d) basis set, with additional single point calculations at the stationary points of the potential energy surface using the (5s4p3d2f/4s3p2d) basis set. These calculations represent the most extensive set of ab initio calculations completed to date, yielding a zero point corrected barrier for HN2 dissociation of approx. 8.5 kcal mol/1. The lifetime of the HN2 species is estimated from the calculated geometries and energetics using both conventional Transition State Theory and a method which utilizes an Eckart barrier to compute one dimensional quantum mechanical tunneling effects. It is concluded that the lifetime of the HN2 species is very short, greatly limiting its role in both termolecular recombination reactions and combustion processes.

  14. Calculation of screened Coulomb potential matrices and its application to He bound and resonant states

    NASA Astrophysics Data System (ADS)

    Jiao, Li Guang; Ho, Yew Kam

    2014-07-01

    We present two analytical methods, Taylor expansion and Gegenbauer expansion, to efficiently and accurately calculate the two-electron screened Coulomb potential matrix elements with Slater-type configuration-interaction basis functions. The former permits great advantages in fast computation of the potential matrices at small screening parameters and the latter allows accurate calculation of the matrices at all screening parameters. The bound and resonant states of a He atom embedded in the screening environment are calculated by employing the variational and complex-scaling methods, respectively, and the results are compared with other theoretical predictions. The expectation values of some physical quantities for He ground state are compared with the recent calculation of Ancarani and Rodriguez [Phys. Rev. A 89, 012507 (2014), 10.1103/PhysRevA.89.012507] and extended to stronger screening environment. The energies and widths for the doubly excited resonant states are in good agreement with previous calculations, while the interelectronic angle arccos show significant discrepancies with the Feshbach projection calculation of Ordóñez-Lasso et al. [Phys. Rev. A 88, 012702 (2013), 10.1103/PhysRevA.88.012702]. The expectation values of are also calculated for the resonant states investigated here. We conclude that the present methods in the framework of complex scaling enable us to get reliable energy, width, and other physical quantities of the resonant states in a variety of screening conditions.

  15. Probing the Adsorption Behavior of 4,5-Diazafluoren-9-one and Its Schiff Base Derivatives on SIlver and Gold Nanosurfaces Using Raman Spectroscopy, Density Functional Theory and Potential Energy Distribution Calculations

    NASA Astrophysics Data System (ADS)

    McCoy, Rhonda Patrice

    4,5-Diazafluoren-9-one (DAFO) is an aromatic ketone synthesized by oxidizing 1,10-phenanthroline with potassium permanganate. In this present study, the Raman spectra of DAFO in the solid and solution states were recorded in the 100-2000 cm-1 spectral region using 1064, 633, 532, and 514 nm excitation sources. A normal mode analysis of DAFO was performed using density functional theory; the BLYP and B3LYP functionals, each with the 6-31G(d) and 6-311(d) basis sets were employed. The fundamental modes on the Raman spectrum of DAFO were assigned with the appropriate symmetry element using the BLYP functional and 6-31G(d) basis set. The vibrational modes were described and quantified by potential energy distribution calculations. The Raman frequencies for the solid and solution spectra were compared; the observed frequency shifts are attributed to hydrogen bonding or dipole-dipole interactions occurring between the solvent and DAFO ligand. To further assess solute-solvent interactions the UV-vis spectra of DAFO was obtained in hydrogen bonding, polar aprotic, and non-polar solvents. The fine structure of the band observed at lambda max becomes more resolved as solvent polarity decreases, therefore confirming solute-solvent interactions in polar solvents. A silver complex of DAFO was synthesized with the intent of understanding how coordination affected the Raman frequencies. The bands assigned to pyridine ring bending, nu(C=N), and nu(C=O) were shifted because of coordination. These shifts have been attributed to the molecule being perturbed because of coordination. Therefore, the Ag-DAFO complex was analyzed by X-Ray diffraction and the molecular geometries of the free and coordinated ligand were compared. The resolved crystalline structure revealed the silver ion coordinated DAFO using the lone pairs of electrons from the nitrogens in the pyridine ring. Analysis of the molecular geometry revealed the C=O bond increases in double bond character and the C5-C14 bond

  16. The potential of renewable energy

    SciTech Connect

    Not Available

    1990-03-01

    On June 27 and 28, 1989, the US Department of Energy (DOE) national laboratories were convened to discuss plans for the development of a National Energy Strategy (NES) and, in particular, the analytic needs in support of NES that could be addressed by the laboratories. As a result of that meeting, interlaboratory teams were formed to produce analytic white papers on key topics, and a lead laboratory was designated for each core laboratory team. The broad-ranging renewables assignment is summarized by the following issue statement from the Office of Policy, Planning and Analysis: to what extent can renewable energy technologies contribute to diversifying sources of energy supply What are the major barriers to greater renewable energy use and what is the potential timing of widespread commercialization for various categories of applications This report presents the results of the intensive activity initiated by the June 1989 meeting to produce a white paper on renewable energy. Scores of scientists, analysts, and engineers in the five core laboratories gave generously of their time over the past eight months to produce this document. Their generous, constructive efforts are hereby gratefully acknowledged. 126 refs., 44 figs., 32 tabs.

  17. Electronic structure calculations toward new potentially AChE inhibitors

    NASA Astrophysics Data System (ADS)

    de Paula, A. A. N.; Martins, J. B. L.; Gargano, R.; dos Santos, M. L.; Romeiro, L. A. S.

    2007-10-01

    The main purpose of this study was the use of natural non-isoprenoid phenolic lipid of cashew nut shell liquid from Anacardium occidentale as lead material for generating new potentially candidates of acetylcholinesterase inhibitors. Therefore, we studied the electronic structure of 15 molecules derivatives from the cardanol using the following groups: methyl, acetyl, N, N-dimethylcarbamoyl, N, N-dimethylamine, N, N-diethylamine, piperidine, pyrrolidine, and N-benzylamine. The calculations were performed at RHF level using 6-31G, 6-31G(d), 6-31+G(d) and 6-311G(d,p) basis functions. Among the proposed compounds we found that the structures with substitution by acetyl, N, N-dimethylcarbamoyl, N, N-dimethylamine, and pyrrolidine groups were better correlated to rivastigmine indicating possible activity.

  18. Calculations of {sup 8}He+p elastic cross sections using a microscopic optical potential

    SciTech Connect

    Lukyanov, V. K.; Zemlyanaya, E. V.; Lukyanov, K. V.; Kadrev, D. N.; Antonov, A. N.; Gaidarov, M. K.; Massen, S. E.

    2009-08-15

    An approach to calculate microscopic optical potential with the real part obtained by a folding procedure and with the imaginary part inherent in the high-energy approximation is applied to study the {sup 8}He+p elastic-scattering data at energies of tens of MeV/nucleon. The neutron and proton density distributions obtained in different models for {sup 8}He are used in the calculations of the differential cross sections. The role of the spin-orbit potential is studied. Comparison of the calculations with the available experimental data on the elastic-scattering differential cross sections at beam energies of 15.7, 26.25, 32, 66, and 73 MeV/nucleon is performed. The problem of the ambiguities of the depths of each component of the optical potential is considered by means of the imposed physical criterion related to the known behavior of the volume integrals as functions of the incident energy. It is shown also that the role of the surface absorption is rather important, in particular for the lowest incident energies (e.g., 15.7 and 26.25 MeV/nucleon)

  19. Photodissociation of methane: Exploring potential energy surfaces

    NASA Astrophysics Data System (ADS)

    van Harrevelt, Rob

    2006-09-01

    The potential energy surface for the first excited singlet state (S1) of methane is explored using multireference singles and doubles configuration interaction calculations, employing a valence triple zeta basis set. A larger valence quadruple zeta basis is used to calculate the vertical excitation energy and dissociation energies. All stationary points found on the S1 surface are saddle points and have imaginary frequencies for symmetry-breaking vibrations. By studying several two-dimensional cuts through the potential energy surfaces, it is argued that CH4 in the S1 state will distort to planar structures. Several conical intersection seams between the ground state surface S0 and the S1 surface have been identified at planar geometries. The conical intersections provide electronically nonadiabatic pathways towards products CH3(X˜A2″2)+H, CH2(ãA11)+H2, or CH2(X˜B13)+H +H. The present results thereby make it plausible that the CH3(X˜A2″2)+H and CH2(ãA11)+H2 channels are major dissociation channels, as has been observed experimentally.

  20. Quantum calculations for rotational energy transfer in nitrogen molecule collisions

    NASA Astrophysics Data System (ADS)

    Huo, Winifred M.; Green, Sheldon

    1996-05-01

    Rotational energy transfer in collisions of nitrogen molecules has been studied theoretically, using the N2-N2 rigid-rotor potential of van der Avoird et al. [J. Chem. Phys. 84, 1629 (1986)]. For benchmarking purposes, converged close coupling (CC) calculations have been carried out to a total energy of about 200 cm-1. Coupled states (CS) approximation calculations have been carried out to a total energy of 680 cm-1, and infinite order sudden (IOS) approximation calculations have also been carried out. The CC and CS cross sections have been obtained both with and without identical molecule exchange symmetry, whereas exchange was neglected in the IOS calculations. The CS results track the CC cross sections rather well: between 113-219 cm-1 the average deviation is 14%, with accuracy improving at higher energy. Comparison between the CS and IOS cross sections at the high energy end of the CS calculations, 500-680 cm-1, shows that IOS is sensitive to the amount of inelasticity and the results for large ΔJ transitions are subject to larger errors. State-to-state cross sections with even and odd exchange symmetry agree to better than 2% and are well represented as a sum of direct and exchange cross sections for distinguishable molecules, an indication of the applicability of a classical treatment for this system. This result, however, does not apply to partial cross sections for given total J, but arises from a near cancellation of the interference terms between even and odd exchange symmetries on summing over partial waves. In order to compare with experimental data for rotational excitation rates of N2 in the n=1 excited vibrational level colliding with ground vibrational level (n=0) bath N2 molecules, it is assumed that exchange scattering between molecules in different vibrational levels is negligible and direct scattering is independent of n so that distinguishable molecule rigid rotor rates may be used. With these assumptions good agreement is obtained. Although

  1. Low-energy calculations for nuclear photodisintegration

    NASA Astrophysics Data System (ADS)

    Deflorian, S.; Efros, V. D.; Leidemann, W.

    2016-03-01

    In the Standard Solar Model a central role in the nucleosynthesis is played by reactions of the kind {}{Z_1}{A_1}{X_1} + {}{Z_2}{A_2}{X_2} to {}{Z_1 + {Z_2}}{A_1 + {A_2}}Y + γ , which enter the proton-proton chains. These reactions can also be studied through the inverse photodisintegration reaction. One option is to use the Lorentz Integral Transform approach, which transforms the continuum problem into a bound state-like one. A way to check the reliability of such methods is a direct calculation, for example using the Kohn Variational Principle to obtain the scattering wave function and then directly calculate the response function of the reaction.

  2. Calculations of Solvation Free Energy through Energy Reweighting from Molecular Mechanics to Quantum Mechanics.

    PubMed

    Jia, Xiangyu; Wang, Meiting; Shao, Yihan; König, Gerhard; Brooks, Bernard R; Zhang, John Z H; Mei, Ye

    2016-02-01

    In this work, the solvation free energies of 20 organic molecules from the 4th Statistical Assessment of the Modeling of Proteins and Ligands (SAMPL4) have been calculated. The sampling of phase space is carried out at a molecular mechanical level, and the associated free energy changes are estimated using the Bennett Acceptance Ratio (BAR). Then the quantum mechanical (QM) corrections are computed through the indirect Non-Boltzmann Bennett's acceptance ratio (NBB) or the thermodynamics perturbation (TP) method. We show that BAR+TP gives a minimum analytic variance for the calculated solvation free energy at the Gaussian limit and performs slightly better than NBB in practice. Furthermore, the expense of the QM calculations in TP is only half of that in NBB. We also show that defining the biasing potential as the difference of the solute-solvent interaction energy, instead of the total energy, can converge the calculated solvation free energies much faster but possibly to different values. Based on the experimental solvation free energies which have been published before, it is discovered in this study that BLYP yields better results than MP2 and some other later functionals such as B3LYP, M06-2X, and ωB97X-D. PMID:26731197

  3. Calculations of Solvation Free Energy through Energy Reweighting from Molecular Mechanics to Quantum Mechanics.

    PubMed

    Jia, Xiangyu; Wang, Meiting; Shao, Yihan; König, Gerhard; Brooks, Bernard R; Zhang, John Z H; Mei, Ye

    2016-02-01

    In this work, the solvation free energies of 20 organic molecules from the 4th Statistical Assessment of the Modeling of Proteins and Ligands (SAMPL4) have been calculated. The sampling of phase space is carried out at a molecular mechanical level, and the associated free energy changes are estimated using the Bennett Acceptance Ratio (BAR). Then the quantum mechanical (QM) corrections are computed through the indirect Non-Boltzmann Bennett's acceptance ratio (NBB) or the thermodynamics perturbation (TP) method. We show that BAR+TP gives a minimum analytic variance for the calculated solvation free energy at the Gaussian limit and performs slightly better than NBB in practice. Furthermore, the expense of the QM calculations in TP is only half of that in NBB. We also show that defining the biasing potential as the difference of the solute-solvent interaction energy, instead of the total energy, can converge the calculated solvation free energies much faster but possibly to different values. Based on the experimental solvation free energies which have been published before, it is discovered in this study that BLYP yields better results than MP2 and some other later functionals such as B3LYP, M06-2X, and ωB97X-D.

  4. Calculating solar photovoltaic potential on residential rooftops in Kailua Kona, Hawaii

    NASA Astrophysics Data System (ADS)

    Carl, Caroline

    As carbon based fossil fuels become increasingly scarce, renewable energy sources are coming to the forefront of policy discussions around the globe. As a result, the State of Hawaii has implemented aggressive goals to achieve energy independence by 2030. Renewable electricity generation using solar photovoltaic technologies plays an important role in these efforts. This study utilizes geographic information systems (GIS) and Light Detection and Ranging (LiDAR) data with statistical analysis to identify how much solar photovoltaic potential exists for residential rooftops in the town of Kailua Kona on Hawaii Island. This study helps to quantify the magnitude of possible solar photovoltaic (PV) potential for Solar World SW260 monocrystalline panels on residential rooftops within the study area. Three main areas were addressed in the execution of this research: (1) modeling solar radiation, (2) estimating available rooftop area, and (3) calculating PV potential from incoming solar radiation. High resolution LiDAR data and Esri's solar modeling tools and were utilized to calculate incoming solar radiation on a sample set of digitized rooftops. Photovoltaic potential for the sample set was then calculated with the equations developed by Suri et al. (2005). Sample set rooftops were analyzed using a statistical model to identify the correlation between rooftop area and lot size. Least squares multiple linear regression analysis was performed to identify the influence of slope, elevation, rooftop area, and lot size on the modeled PV potential values. The equations built from these statistical analyses of the sample set were applied to the entire study region to calculate total rooftop area and PV potential. The total study area statistical analysis findings estimate photovoltaic electric energy generation potential for rooftops is approximately 190,000,000 kWh annually. This is approximately 17 percent of the total electricity the utility provided to the entire island in

  5. Computed potential energy surfaces for chemical reactions

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    1994-01-01

    Quantum mechanical methods have been used to compute potential energy surfaces for chemical reactions. The reactions studied were among those believed to be important to the NASP and HSR programs and included the recombination of two H atoms with several different third bodies; the reactions in the thermal Zeldovich mechanism; the reactions of H atom with O2, N2, and NO; reactions involved in the thermal De-NO(x) process; and the reaction of CH(squared Pi) with N2 (leading to 'prompt NO'). These potential energy surfaces have been used to compute reaction rate constants and rates of unimolecular decomposition. An additional application was the calculation of transport properties of gases using a semiclassical approximation (and in the case of interactions involving hydrogen inclusion of quantum mechanical effects).

  6. Calculation of energy deposition distributions for simple geometries

    NASA Technical Reports Server (NTRS)

    Watts, J. W., Jr.

    1973-01-01

    When high-energy charged particles pass through a thin detector, the ionization energy loss in that detector is subject to fluctuations or straggling which must be considered in interpreting the data. Under many conditions, which depend upon the charge and energy of the incident particle and the detector geometry, the ionization energy lost by the particle is significantly different from the energy deposited in the detector. This problem divides naturally into a calculation of the energy loss that results in excitation and low-energy secondary electrons which do not travel far from their production points, and a calculation of energy loss that results in high-energy secondary electrons which can escape from the detector. The first calculation is performed using a modification of the Vavilov energy loss distribution. A cutoff energy is introduced above which all electrons are ignored and energy transferred to low energy particles is assumed to be equivalent to the energy deposited by them. For the second calculation, the trajectory of the primary particle is considered as a source of secondary high-energy electrons. The electrons from this source are transported using Monte Carlo techniques and multiple scattering theory, and the energy deposited by them in the detector is calculated. The results of the two calculations are then combined to predict the energy deposition distribution. The results of these calculations are used to predict the charge resolution of parallel-plate pulse ionization chambers that are being designed to measure the charge spectrum of heavy nuclei in the galactic cosmic-ray flux.

  7. Three-body calculations for the K - pp system within potential models

    NASA Astrophysics Data System (ADS)

    Kezerashvili, R. Ya; Tsiklauri, S. M.; Filikhin, I.; Suslov, V. M.; Vlahovic, B.

    2016-06-01

    We present three-body nonrelativistic calculations within the framework of a potential model for the kaonic cluster K - pp using two methods: the method of hyperspherical harmonics in the momentum representation and the method of Faddeev equations in configuration space. To perform numerical calculations, different NN and antikaon-nucleon interactions are applied. The results of the calculations for the ground-state energy for the K - pp system obtained by both methods are in reasonable agreement. Although the ground-state energy is not sensitive to the pp interaction, it shows very strong dependence on the K - p potential. We show that the dominant clustering of the {K}-{pp} system in the configuration Λ (1405) + p allows us to calculate the binding energy to good accuracy within a simple cluster approach for the differential Faddeev equations. The theoretical discrepancies in the binding energy and width for the K - pp system related to the different pp and K - p interactions are addressed.

  8. Three-body calculations for the K ‑ pp system within potential models

    NASA Astrophysics Data System (ADS)

    Kezerashvili, R. Ya; Tsiklauri, S. M.; Filikhin, I.; Suslov, V. M.; Vlahovic, B.

    2016-06-01

    We present three-body nonrelativistic calculations within the framework of a potential model for the kaonic cluster K ‑ pp using two methods: the method of hyperspherical harmonics in the momentum representation and the method of Faddeev equations in configuration space. To perform numerical calculations, different NN and antikaon–nucleon interactions are applied. The results of the calculations for the ground-state energy for the K ‑ pp system obtained by both methods are in reasonable agreement. Although the ground-state energy is not sensitive to the pp interaction, it shows very strong dependence on the K ‑ p potential. We show that the dominant clustering of the {K}-{pp} system in the configuration Λ (1405) + p allows us to calculate the binding energy to good accuracy within a simple cluster approach for the differential Faddeev equations. The theoretical discrepancies in the binding energy and width for the K ‑ pp system related to the different pp and K ‑ p interactions are addressed.

  9. Potential energy surfaces of Polonium isotopes

    NASA Astrophysics Data System (ADS)

    Nerlo-Pomorska, B.; Pomorski, K.; Schmitt, C.; Bartel, J.

    2015-11-01

    The evolution of the potential energy landscape is analysed in detail for ten even-even polonium isotopes in the mass range 188\\lt A\\lt 220 as obtained within the macroscopic-microscopic approach, relying on the Lublin-Strasbourg drop model and the Yukawa-folded single-particle energies for calculating the microscopic shell and pairing corrections. A variant of the modified Funny-Hills nuclear shape parametrization is used to efficiently map possible fission paths. The approach explains the main features of the fragment partition as measured in low-energy fission along the polonium chain. The latter lies in a transitional region of the nuclear chart, and will be essential to consistently understand the evolution of fission properties from neutron-deficient mercury to heavy actinides. The ability of our method to predict fission observables over such an extended region looks promising.

  10. Separable Potentials for (d,p) Reaction Calculations

    NASA Astrophysics Data System (ADS)

    Elster, Ch.; Hlophe, L.; Eremenko, V.; Nunes, F. M.; Thompson, I. J.; Arbanas, G.; Escher, J. E.

    2016-06-01

    An important ingredient for applications of nuclear physics to e.g. astrophysics or nuclear energy are the cross sections for reactions of neutrons with rare isotopes. Since direct measurements are often not possible, indirect methods like (d,p) reactions must be used instead. Those (d,p) reactions may be viewed as effective three-body reactions and described with Faddeev techniques. An additional challenge posed by (d,p) reactions involving heavier nuclei is the treatment of the Coulomb force. To avoid numerical complications in dealing with the screening of the Coulomb force, recently a new approach using the Coulomb distorted basis in momentum space was suggested. In order to implement this suggestion, one needs to derive a separable representation of neutron- and proton-nucleus optical potentials and compute their matrix elements in this basis.

  11. Ionization potential of {sup 9}Be calculated including nuclear motion and relativistic corrections

    SciTech Connect

    Stanke, Monika; Kedziera, Dariusz; Bubin, Sergiy; Adamowicz, Ludwik

    2007-05-15

    Variational calculations employing explicitly correlated Gaussian functions have been performed for the ground states of {sup 9}Be and {sup 9}Be{sup +} including the nuclear motion [i.e., without assuming the Born-Oppenheimer (BO) approximation]. An approach based on the analytical energy gradient calculated with respect to the Gaussian exponential parameters was employed, leading to energies of the two systems noticeably improved over those found in the recent paper of Pachucki and Komasa [Phys. Rev. A 73, 052502 (2006)]. The non-BO wave functions were used to calculate the {alpha}{sup 2} relativistic corrections ({alpha}=e{sup 2}/({Dirac_h}/2{pi})c). With those corrections and the {alpha}{sup 3} and {alpha}{sup 4} corrections taken from Pachucki and Komasa, a new value of the ionization potential (IP) of {sup 9}Be was determined. It agrees very well with the most recent experimental IP.

  12. Sensitivity of methods for calculating energy expenditure by use of doubly labeled water

    SciTech Connect

    Seale, J.; Miles, C.; Bodwell, C.E.

    1989-02-01

    Attempts to estimate human energy expenditure by use of doubly labeled water have produced three methods currently used for calculating carbon dioxide production from isotope disappearance data: (1) the two-point method, (2) the regression method, and (3) the integration method. An ideal data set was used to determine the error produced in the calculated energy expenditure for each method when specific variables were perturbed. The analysis indicates that some of the calculation methods are more susceptible to perturbations in certain variables than others. Results from an experiment on one adult human subject are used to illustrate the potential for error in actual data. Samples of second void urine, 24-h urine, and breath collected every other day for 21 days are used to calculate the average daily energy expenditure by three calculation methods. The difference between calculated energy expenditure and metabolizable energy on a weight-maintenance diet is used to estimate the error associated with the doubly labeled water method.

  13. Density functional theory for comprehensive orbital energy calculations.

    PubMed

    Nakata, Ayako; Tsuneda, Takao

    2013-08-14

    This study reveals the reason core 1s orbital energies and the highest occupied molecular orbital (HOMO) energies of hydrogen and rare gas atoms are underestimated by long-range corrected (LC) density functional theory (DFT), which quantitatively reproduces the HOMO energies of other systems and the lowest unoccupied molecular orbital (LUMO) energies. Applying the pseudospectral regional (PR) self-interaction correction (SIC) drastically improved the underestimated orbital energies in LC-DFT calculations, while maintaining or improving the accuracies in the calculated valence HOMO and LUMO energies. This indicates that the self-interaction error in exchange functionals causes the underestimations of core 1s orbital energies and the HOMO energies of hydrogen and rare gas atoms in LC-DFT calculations. To clarify the reason for the improvement, the fractional occupation dependences of total electronic energies and orbital energies were examined. The calculated results clearly showed that the LC-PR functional gives almost linear dependences of total electronic energies for a slight decrease in the occupation number of core 1s orbitals, although this linear dependence disappears for significant decrease due to the shrinking of exchange self-interaction regions. It was also clarified that the PRSIC hardly affects the occupation number dependences of the total electronic energies and orbital energies for the fractional occupations of HOMOs and LUMOs. As a result, it was concluded that core orbital energies are obtained accurately by combining LC-DFT with PRSIC.

  14. Ab initio calculations of free-energy reaction barriers.

    PubMed

    Bucko, T

    2008-02-13

    The theoretical description of chemical reactions was until recently limited to a 'static' approach in which important parameters such as the rate constant are deduced from the local topology of the potential energy surface close to minima and saddle points. Such an approach has, however, serious limitations. The growing computational power allows us now to use advanced simulation techniques to determine entropic effects accurately for medium-sized systems at ab initio level. Recently, we have implemented free-energy simulation techniques based on molecular dynamics, in particular on the blue-moon ensemble technique and on metadynamics, in the popular DFT code VASP. In the thermodynamic integration (blue-moon ensemble) technique, the free-energy profile is calculated as the path integral over the restoring forces along a parametrized reaction coordinate. In metadynamics, an image of the free-energy surface is constructed on the fly during the simulation by adding small repulsive Gaussian-shaped hills to the Lagrangian driving the dynamics. The two methods are tested on a simple chemical reaction-the nucleophilic substitution of methyl chloride by a chlorine anion.

  15. Ab initio calculations of free-energy reaction barriers

    NASA Astrophysics Data System (ADS)

    Bucko, T.

    2008-02-01

    The theoretical description of chemical reactions was until recently limited to a 'static' approach in which important parameters such as the rate constant are deduced from the local topology of the potential energy surface close to minima and saddle points. Such an approach has, however, serious limitations. The growing computational power allows us now to use advanced simulation techniques to determine entropic effects accurately for medium-sized systems at ab initio level. Recently, we have implemented free-energy simulation techniques based on molecular dynamics, in particular on the blue-moon ensemble technique and on metadynamics, in the popular DFT code VASP. In the thermodynamic integration (blue-moon ensemble) technique, the free-energy profile is calculated as the path integral over the restoring forces along a parametrized reaction coordinate. In metadynamics, an image of the free-energy surface is constructed on the fly during the simulation by adding small repulsive Gaussian-shaped hills to the Lagrangian driving the dynamics. The two methods are tested on a simple chemical reaction—the nucleophilic substitution of methyl chloride by a chlorine anion.

  16. Convective Available Potential Energy of World Ocean

    NASA Astrophysics Data System (ADS)

    Su, Z.; Ingersoll, A. P.; Thompson, A. F.

    2012-12-01

    Here, for the first time, we propose the concept of Ocean Convective Available Potential Energy (OCAPE), which is the maximum kinetic energy (KE) per unit seawater mass achievable by ocean convection. OCAPE occurs through a different mechanism from atmospheric CAPE, and involves the interplay of temperature and salinity on the equation of state of seawater. The thermobaric effect, which arises because the thermal coefficient of expansion increases with depth, is an important ingredient of OCAPE. We develop an accurate algorithm to calculate the OCAPE for a given temperature and salinity profile. We then validate our calculation of OCAPE by comparing it with the conversion of OCAPE to KE in a 2-D numerical model. We propose that OCAPE is an important energy source of ocean deep convection and contributes to deep water formation. OCAPE, like Atmospheric CAPE, can help predict deep convection and may also provide a useful constraint for modelling deep convection in ocean GCMs. We plot the global distribution of OCAPE using data from the World Ocean Atlas 2009 (WOA09) and see many important features. These include large values of OCAPE in the Labrador, Greenland, Weddell and Mediterranean Seas, which are consistent with our present observations and understanding, but also identify some new features like the OCAPE pattern in the Antarctic Circumpolar Current (ACC). We propose that the diagnosis of OCAPE can improve our understanding of global patterns of ocean convection and deep water formation as well as ocean stratification, the meridional overturning circulation and mixed layer processes. The background of this work is briefly introduced as below. Open-ocean deep convection can significantly modify water properties both at the ocean surface and throughout the water column (Gordon 1982). Open-ocean convection is also an important mechanism for Ocean Deep Water formation and the transport of heat, freshwater and nutrient (Marshall and Schott 1999). Open

  17. Energy deposition calculated by PHITS code in Pb spallation target

    NASA Astrophysics Data System (ADS)

    Yu, Quanzhi

    2016-01-01

    Energy deposition in a Pb spallation target irradiated by high energetic protons was calculated by PHITS2.52 code. The validation of the energy deposition and neutron production calculated by PHITS code was performed. Results show good agreements between the simulation results and the experimental data. Detailed comparison shows that for the total energy deposition, PHITS simulation result was about 15% overestimation than that of the experimental data. For the energy deposition along the length of the Pb target, the discrepancy mainly presented at the front part of the Pb target. Calculation indicates that most of the energy deposition comes from the ionizations of the primary protons and the produced secondary particles. With the event generator mode of PHITS, the deposit energy distribution for the particles and the light nulclei is presented for the first time. It indicates that the primary protons with energy more than 100 MeV are the most contributors to the total energy deposition. The energy depositions peaking at 10 MeV and 0.1 MeV, are mainly caused by the electrons, pions, d, t, 3He and also α particles during the cascade process and the evaporation process, respectively. The energy deposition density caused by different proton beam profiles are also calculated and compared. Such calculation and analyses are much helpful for better understanding the physical mechanism of energy deposition in the spallation target, and greatly useful for the thermal hydraulic design of the spallation target.

  18. Heuristic control of kinetic energy in dynamic reaction coordinate calculations.

    PubMed

    Hellweg, Arnim

    2013-08-01

    For the understanding and prediction of chemical reactions, detailed knowledge of the minimum energy path between reactants and transition state is of utmost importance. Stewart et al. (J. Comput. Chem. 1987, 8, 1117) proposed the usage of molecular trajectories calculated from Newton's equations of motion for an efficient reaction path following. Two operational modes are possible thereby: intrinsic (IRC) and dynamic reaction coordinate calculations (DRC). The technical difference between these modes is that in an IRC calculation the kinetic energy of the nuclei is quenched while the total energy is conserved in DRC calculations. In this work, a heuristic control methodology of atomic kinetic energies in DRC calculations using fuzzy logic is proposed. A diversified test set of 10 reactions has been collected to examine the performance of this approach. Fuzzy rule-based models are found to be a convenient way to make the determination of accessible paths of chemical reactions computationally efficient.

  19. Guidelines for the analysis of free energy calculations

    PubMed Central

    Klimovich, Pavel V.; Shirts, Michael R.; Mobley, David L.

    2015-01-01

    Free energy calculations based on molecular dynamics (MD) simulations show considerable promise for applications ranging from drug discovery to prediction of physical properties and structure-function studies. But these calculations are still difficult and tedious to analyze, and best practices for analysis are not well defined or propagated. Essentially, each group analyzing these calculations needs to decide how to conduct the analysis and, usually, develop its own analysis tools. Here, we review and recommend best practices for analysis yielding reliable free energies from molecular simulations. Additionally, we provide a Python tool, alchemical–analysis.py, freely available on GitHub at https://github.com/choderalab/pymbar–examples, that implements the analysis practices reviewed here for several reference simulation packages, which can be adapted to handle data from other packages. Both this review and the tool covers analysis of alchemical calculations generally, including free energy estimates via both thermodynamic integration and free energy perturbation-based estimators. Our Python tool also handles output from multiple types of free energy calculations, including expanded ensemble and Hamiltonian replica exchange, as well as standard fixed ensemble calculations. We also survey a range of statistical and graphical ways of assessing the quality of the data and free energy estimates, and provide prototypes of these in our tool. We hope these tools and discussion will serve as a foundation for more standardization of and agreement on best practices for analysis of free energy calculations. PMID:25808134

  20. Guidelines for the analysis of free energy calculations.

    PubMed

    Klimovich, Pavel V; Shirts, Michael R; Mobley, David L

    2015-05-01

    Free energy calculations based on molecular dynamics simulations show considerable promise for applications ranging from drug discovery to prediction of physical properties and structure-function studies. But these calculations are still difficult and tedious to analyze, and best practices for analysis are not well defined or propagated. Essentially, each group analyzing these calculations needs to decide how to conduct the analysis and, usually, develop its own analysis tools. Here, we review and recommend best practices for analysis yielding reliable free energies from molecular simulations. Additionally, we provide a Python tool, alchemical-analysis.py, freely available on GitHub as part of the pymbar package (located at http://github.com/choderalab/pymbar), that implements the analysis practices reviewed here for several reference simulation packages, which can be adapted to handle data from other packages. Both this review and the tool covers analysis of alchemical calculations generally, including free energy estimates via both thermodynamic integration and free energy perturbation-based estimators. Our Python tool also handles output from multiple types of free energy calculations, including expanded ensemble and Hamiltonian replica exchange, as well as standard fixed ensemble calculations. We also survey a range of statistical and graphical ways of assessing the quality of the data and free energy estimates, and provide prototypes of these in our tool. We hope this tool and discussion will serve as a foundation for more standardization of and agreement on best practices for analysis of free energy calculations.

  1. A Frontier orbital energy approach to redox potentials

    NASA Astrophysics Data System (ADS)

    Conradie, Jeanet

    2015-09-01

    The prediction of the oxidation and reduction potentials of molecules is important in many research areas. A review of relationships obtained between frontier orbital energies (eV), the calculated ionization potentials (IP in eV), or adiabatic electron affinities (EA in eV) with the experimental oxidation and reduction potentials is presented, for selected series of β- diketones, rhodium-β-diketonato complexes, as well as metal-tris-β-diketonato complexes, with the metal Fe or Mn. The good linear relationships obtained for related series of complexes show that the oxidation and reduction potentials of these complexes can be predicted by their DFT-calculated energies.

  2. Free energies of binding from large-scale first-principles quantum mechanical calculations: application to ligand hydration energies.

    PubMed

    Fox, Stephen J; Pittock, Chris; Tautermann, Christofer S; Fox, Thomas; Christ, Clara; Malcolm, N O J; Essex, Jonathan W; Skylaris, Chris-Kriton

    2013-08-15

    Schemes of increasing sophistication for obtaining free energies of binding have been developed over the years, where configurational sampling is used to include the all-important entropic contributions to the free energies. However, the quality of the results will also depend on the accuracy with which the intermolecular interactions are computed at each molecular configuration. In this context, the energy change associated with the rearrangement of electrons (electronic polarization and charge transfer) upon binding is a very important effect. Classical molecular mechanics force fields do not take this effect into account explicitly, and polarizable force fields and semiempirical quantum or hybrid quantum-classical (QM/MM) calculations are increasingly employed (at higher computational cost) to compute intermolecular interactions in free-energy schemes. In this work, we investigate the use of large-scale quantum mechanical calculations from first-principles as a way of fully taking into account electronic effects in free-energy calculations. We employ a one-step free-energy perturbation (FEP) scheme from a molecular mechanical (MM) potential to a quantum mechanical (QM) potential as a correction to thermodynamic integration calculations within the MM potential. We use this approach to calculate relative free energies of hydration of small aromatic molecules. Our quantum calculations are performed on multiple configurations from classical molecular dynamics simulations. The quantum energy of each configuration is obtained from density functional theory calculations with a near-complete psinc basis set on over 600 atoms using the ONETEP program.

  3. Ab initio Potential Energy Surface for H-H2

    NASA Technical Reports Server (NTRS)

    Partridge, Harry; Bauschlicher, Charles W., Jr.; Stallcop, James R.; Levin, Eugene

    1993-01-01

    Ab initio calculations employing large basis sets are performed to determine an accurate potential energy surface for H-H2 interactions for a broad range of separation distances. At large distances, the spherically averaged potential determined from the calculated energies agrees well with the corresponding results determined from dispersion coefficients; the van der Waals well depth is predicted to be 75 +/- (mu)E(sub h). Large basis sets have also been applied to reexamine the accuracy of theoretical repulsive potential energy surfaces. Multipolar expansions of the computed H-H2 potential energy surface are reported for four internuclear separation distances (1.2, 1.401, 1.449, and 1.7a(sub 0) of the hydrogen molecule. The differential elastic scattering cross section calculated from the present results is compared with the measurements from a crossed beam experiment.

  4. 18 CFR 11.13 - Energy gains calculations.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 18 Conservation of Power and Water Resources 1 2011-04-01 2011-04-01 false Energy gains calculations. 11.13 Section 11.13 Conservation of Power and Water Resources FEDERAL ENERGY REGULATORY COMMISSION, DEPARTMENT OF ENERGY REGULATIONS UNDER THE FEDERAL POWER ACT ANNUAL CHARGES UNDER PART I OF...

  5. 18 CFR 11.13 - Energy gains calculations.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 18 Conservation of Power and Water Resources 1 2013-04-01 2013-04-01 false Energy gains calculations. 11.13 Section 11.13 Conservation of Power and Water Resources FEDERAL ENERGY REGULATORY COMMISSION, DEPARTMENT OF ENERGY REGULATIONS UNDER THE FEDERAL POWER ACT ANNUAL CHARGES UNDER PART I OF...

  6. 18 CFR 11.13 - Energy gains calculations.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 18 Conservation of Power and Water Resources 1 2014-04-01 2014-04-01 false Energy gains calculations. 11.13 Section 11.13 Conservation of Power and Water Resources FEDERAL ENERGY REGULATORY COMMISSION, DEPARTMENT OF ENERGY REGULATIONS UNDER THE FEDERAL POWER ACT ANNUAL CHARGES UNDER PART I OF...

  7. 18 CFR 11.13 - Energy gains calculations.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 18 Conservation of Power and Water Resources 1 2010-04-01 2010-04-01 false Energy gains calculations. 11.13 Section 11.13 Conservation of Power and Water Resources FEDERAL ENERGY REGULATORY COMMISSION, DEPARTMENT OF ENERGY REGULATIONS UNDER THE FEDERAL POWER ACT ANNUAL CHARGES UNDER PART I OF...

  8. 18 CFR 11.13 - Energy gains calculations.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 18 Conservation of Power and Water Resources 1 2012-04-01 2012-04-01 false Energy gains calculations. 11.13 Section 11.13 Conservation of Power and Water Resources FEDERAL ENERGY REGULATORY COMMISSION, DEPARTMENT OF ENERGY REGULATIONS UNDER THE FEDERAL POWER ACT ANNUAL CHARGES UNDER PART I OF...

  9. Nonintuitive Diabatic Potential Energy Surfaces for Thioanisole.

    PubMed

    Li, Shaohong L; Xu, Xuefei; Hoyer, Chad E; Truhlar, Donald G

    2015-09-01

    Diabatization of potential energy surfaces is a technique that enables convenient molecular dynamics simulations of electronically nonadiabatic processes, but diabatization itself is nonunique and can be inconvenient; the best methods to achieve diabatization are still under study. Here, we present the diabatization of two electronic states of thioanisole in the S-CH3 bond stretching and C-C-S-C torsion two-dimensional nuclear coordinate space containing a conical intersection. We use two systematic methods: the (orbital-dependent) 4-fold way and the (orbital-free) Boys localization diabatization method. These very different methods yield strikingly similar diabatic potential energy surfaces that cross at geometries where the adiabatic surfaces are well separated and do not exhibit avoided crossings, and the contours of the diabatic gap and diabatic coupling are similar for the two methods. The validity of the diabatization is supported by comparing the nonadiabatic couplings calculated from the diabatic matrix elements to those calculated by direct differentiation of the adiabatic states.

  10. Quantum Calculations on Salt Bridges with Water: Potentials, Structure, and Properties

    SciTech Connect

    Liao, Sing; Green, Michael E.

    2011-01-01

    Salt bridges are electrostatic links between acidic and basic amino acids in a protein; quantum calculations are used here to determine the energetics and other properties of one form of these species, in the presence of water molecules. The acidic groups are carboxylic acids (aspartic and glutamic acids); proteins have two bases with pK above physiological pH: one, arginine, with a guanidinium basic group, the other lysine, which is a primary amine. Only arginine is modeled here, by ethyl guanidinium, while propionic acid is used as a model for either carboxylic acid. The salt bridges are accompanied by 0-12 water molecules; for each of the 13 systems, the energy-bond distance relation, natural bond orbitals (NBO), frequency calculations allowing thermodynamic corrections to room temperature, and dielectric constant dependence, were all calculated. The water molecules were found to arrange themselves in hydrogen bonded rings anchored to the oxygens of the salt bridge components. This was not surprising in itself, but it was found that the rings lead to a periodicity in the energy, and to a 'water addition' rule. The latter shows that the initial rings, with four oxygen atoms, become five member rings when an additional water molecule becomes available, with the additional water filling in at the bond with the lowest Wiberg index, as calculated using NBO. The dielectric constant dependence is the expected hyperbola, and the fit of the energy to the inverse dielectric constant is determined. There is an energy periodicity related to ring formation upon addition of water molecules. When 10 water molecules have been added, all spaces near the salt bridge are filled, completing the first hydration shell, and a second shell starts to form. The potentials associated with salt bridges depend on their hydration, and potentials assigned without regard to local hydration are likely to cause errors as large as or larger than kBT, thus suggesting a serious problem if these

  11. Calculations supporting evaluation of potential environmental standards for Yucca Mountain

    SciTech Connect

    Duguid, J.O.; Andrews, R.W.; Brandstetter, E.; Dale, T.F.; Reeves, M.

    1994-04-01

    The Energy Policy Act of 1992, Section 801 (US Congress, 1992) provides for the US Environmental Protection Agency (EPA) to contract the National Academy of Sciences (NAS) to conduct a study and provide findings and recommendations on reasonable standards for the disposal of high-level wastes at the Yucca Mountain site. The NAS study is to provide findings and recommendations which include, among other things, whether a health-based standard based on dose to individual members of the public from releases to the accessible environment will provide a reasonable standard for the protection of the health and safety of the public. The EPA, based upon and consistent with the findings and recommendations of the NAS, is required to promulgate standards for protection of the public from releases from radioactive materials stored or disposed of in a repository at the Yucca Mountain site. This document presents a number of different ``simple`` analyses of undisturbed repository performance that are intended to provide input to those responsible for setting appropriate environmental standards for a potential repository at the Yucca Mountain site in Nevada. Each of the processes included in the analyses has been simplified to capture the primary significance of that process in containing or isolating the waste from the biosphere. In these simplified analyses, the complex waste package interactions were approximated by a simple waste package ``failure`` distribution which is defined by the initiation and rate of waste package ``failures``. Similarly, releases from the waste package and the engineered barrier system are controlled by the very near field environment and the presence and rate of advective and diffusive release processes. Release was approximated by either a simple alteration-controlled release for the high solubility radionuclides and either a diffusive or advective-controlled release for the solubility-limited radionuclides.

  12. Solid-liquid phase equilibria from free-energy perturbation calculations

    NASA Astrophysics Data System (ADS)

    Angioletti-Uberti, Stefano; Asta, Mark; Finnis, Mike W.; Lee, P. D.

    2008-10-01

    A method for calculating free-energy differences based on a free-energy perturbation (FEP) formalism in an alloy system described by two different Hamiltonians is reported. The intended application is the calculation of solid-liquid phase equilibria in alloys with the accuracy of first-principles electronic density-functional theory (DFT). For this purpose free energies are derived with a classical interatomic potential, and FEP calculations are used to compute corrections to these reference values. For practical applications of this approach, due to the relatively high computational cost of DFT calculations, it is critical that the FEP calculations converge rapidly in terms of the number of samples used to estimate relevant ensemble averages. This issue is investigated in the current study employing two classical interatomic-potential models for Ni-Cu. These models yield differences in predicted phase-boundary temperatures of approximately 100 K, comparable to those that might be expected between a DFT Hamiltonian and a well-fit classical potential. We show that for pure elements the FEP calculations converge rapidly with the number of samples, yielding free-energy differences converged to within a fraction of a meV/atom in a few dozen energy calculations. For a concentrated equiatomic alloy similar precision requires roughly a hundred samples. The results suggest that the proposed methodology could provide a computationally tractable framework for calculating solid-liquid phase equilibria in concentrated alloys with DFT accuracy.

  13. Theoretical characterization of the potential energy surface for NH + NO

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    1993-01-01

    The potential energy surface for NH + NO was characterized using complete active space self-consistent field (CASSCF) gradient calculation to determine the stationary point geometries and frequencies followed by CASSCF/internally contracted configuration interaction calculations to refine the energetics. The present results are in qualitative accord with the BAC-MP4 calculations, but there are differences as large as 8 kcal/mol in the detailed energetics.

  14. MCSCF potential energy surface for photodissociation of formaldehyde

    NASA Technical Reports Server (NTRS)

    Jaffe, R. L.; Morokuma, K.

    1976-01-01

    The ground state potential energy surface for the dissociation of formaldehyde (H2CO to H2 and CO) is calculated with the ab initio MCSCF method with an extended (4-31G) basis set. The location, barrier height, and force constants of the transition state are determined, and the normal coordinate analysis is carried out. The calculated barrier height is 4.5 eV. Based on the calculated quantities, the detailed mechanism of the photochemical dissociation is discussed.

  15. Search for dark energy potentials in quintessence

    NASA Astrophysics Data System (ADS)

    Muromachi, Yusuke; Okabayashi, Akira; Okada, Daiki; Hara, Tetsuya; Itoh, Yutaka

    2015-09-01

    The time evolution of the equation of state w for quintessence models with a scalar field as dark energy is studied up to the third derivative big (d^3w/da^3big ) with respect to the scale factor a, in order to predict future observations and specify the scalar potential parameters with the observables. The third derivative of w for general potential V is derived and applied to several types of potentials. They are the inverse power law big (V=M^{4+α }/Q^{α }big ), the exponential big (V=M^4exp {β M/Q}big ), the mixed big (V=M^{4+γ }exp {β M/Q}/Q^{γ }big ), the cosine big (V=M^4[cos (Q/f)+1]big ), and the Gaussian types big (V=M^4exp big {-Q^2/σ ^2big }big ), which are prototypical potentials for the freezing and thawing models. If the parameter number for a potential form is n, it is necessary to find at least n+2 independent observations to identify the potential form and the evolution of the scalar field (Q and dot {Q}). Such observations would be the values of Ω _Q, w, dw/da,ldots , dw^n/da^n. From these specific potentials, we can predict the n+1 and higher derivatives of w: dw^{n+1}/da^{n+1},ldots . Since four of the abovementioned potentials have two parameters, it is necessary to calculate the third derivative of w for them to estimate the predicted values. If they are tested observationally, it will be understood whether the dark energy can be described by a scalar field with this potential. At least it will satisfy the necessary conditions. Numerical analysis for d^3w/da^3 is performed with some specified parameters in the investigated potentials, except for the mixed one. It becomes possible to distinguish the potentials by accurately observing dw/da and d^2w/da^2 for some parameters.

  16. QED calculation of the ground-state energy of berylliumlike ions

    NASA Astrophysics Data System (ADS)

    Malyshev, A. V.; Volotka, A. V.; Glazov, D. A.; Tupitsyn, I. I.; Shabaev, V. M.; Plunien, G.

    2014-12-01

    Ab initio QED calculations of the ground-state binding energies of berylliumlike ions are performed for the wide range of the nuclear charge number: Z =18 -96 . The calculations are carried out in the framework of the extended Furry picture starting with three different types of the screening potential. The rigorous QED calculations up to the second order of the perturbation theory are combined with the third- and higher-order electron-correlation contributions obtained within the Breit approximation by the use of the large-scale configuration-interaction Dirac-Fock-Sturm method. The effects of nuclear recoil and nuclear polarization are taken into account. The ionization potentials are obtained by subtracting the binding energies of the corresponding lithiumlike ions. In comparison with the previous calculations the accuracy of the binding energies and the ionization potentials is significantly improved.

  17. The Wind Energy Potential of Iceland

    NASA Astrophysics Data System (ADS)

    Nawri, Nikolai; Nína Petersen, Guðrún; Bjornsson, Halldór; Hahmann, Andrea N.; Jónasson, Kristján; Bay Hasager, Charlotte; Clausen, Niels-Erik

    2014-05-01

    infrastructure and the power grid, as well as due to the harsh winter climate. However, even in easily accessible regions, wind energy potential in Iceland, as measured by annual average power density, is among the highest in Western Europe. Based on these results, 14 test sites were selected for more detailed analyses using the Wind Atlas Analysis and Application Program (WAsP). These calculations show that a modest wind farm of ten medium size turbines would produce more energy throughout the year than a small hydro power plant, making wind energy a viable additional option.

  18. Gamma-point lattice free energy estimates from O1 force calculations.

    PubMed

    Voss, Johannes; Vegge, Tejs

    2008-05-14

    We present a new method for estimating the vibrational free energy of crystal (and molecular) structures employing only a single force calculation, for a particularly displaced configuration, in addition to the calculation of the ground state configuration. This displacement vector is the sum of the phonon eigenvectors obtained from a fast-relative to, e.g., density-functional theory (DFT)-Hessian calculation using interatomic potentials. These potentials are based here on effective charges obtained from a DFT calculation of the ground state electronic charge density but could also be based on other, e.g., empiric approaches.

  19. Ab initio calculations of free energy barriers for chemical reactions in solution: proton transfer in [FHF]-.

    PubMed

    Muller, R P; Warshel, A

    1996-01-01

    This paper describes a hybrid ab initio quantum mechanical/molecular mechanics (QM/MM) method for calculating activation free energies of chemical reactions in solution, using molecular mechanics force fields for the solvent and an ab initio technique that incorporates the potential from the solvent in its Hamiltonian for the solute. The empirical valence bond (EVB) method is used as a reference potential for the ab initio free energy calculation, and drives the reaction along the proper coordinate, thus overcoming problems encountered by direct attempts to use molecular orbital methods in calculations of activation free energies. The utility of our method is illustrated by calculating the activation free energy for proton transfer between fluoride ions in the [FHF]-system, in both polar and nonpolar solution.

  20. Wind Energy Finance (WEF): An Online Calculator for Economic Analysis of Wind Projects

    SciTech Connect

    Not Available

    2004-02-01

    This brochure provides an overview of Wind Energy Finance (WEF), a free online cost of energy calculator developed by the National Renewable Energy Laboratory that provides quick, detailed economic evaluation of potential utility-scale wind energy projects. The brochure lists the features of the tool, the inputs and outputs that a user can expect, visuals of the screens and a Cash Flow Results table, and contact information.

  1. Molecular modeling study of chiral drug crystals: lattice energy calculations.

    PubMed

    Li, Z J; Ojala, W H; Grant, D J

    2001-10-01

    The lattice energies of a number of chiral drugs with known crystal structures were calculated using Dreiding II force field. The lattice energies, including van der Waals, Coulombic, and hydrogen-bonding energies, of homochiral and racemic crystals of some ephedrine derivatives and of several other chiral drugs, are compared. The calculated energies are correlated with experimental data to probe the underlying intermolecular forces responsible for the formation of racemic species, racemic conglomerates, or racemic compounds, termed chiral discrimination. Comparison of the calculated energies among ephedrine derivatives reveals that a greater Coulombic energy corresponds to a higher melting temperature, while a greater van der Waals energy corresponds to a larger enthalpy of fusion. For seven pairs of homochiral and racemic compounds, correlation of the differences between the two forms in the calculated energies and experimental enthalpy of fusion suggests that the van der Waals interactions play a key role in the chiral discrimination in the crystalline state. For salts of the chiral drugs, the counter ions diminish chiral discrimination by increasing the Coulombic interactions. This result may explain why salt forms favor the formation of racemic conglomerates, thereby facilitating the resolution of racemates.

  2. Dissociative electron transfer in polychlorinated aromatics. Reduction potentials from convolution analysis and quantum chemical calculations.

    PubMed

    Romańczyk, Piotr P; Rotko, Grzegorz; Kurek, Stefan S

    2016-08-10

    Formal potentials of the first reduction leading to dechlorination in dimethylformamide were obtained from convolution analysis of voltammetric data and confirmed by quantum chemical calculations for a series of polychlorinated benzenes: hexachlorobenzene (-2.02 V vs. Fc(+)/Fc), pentachloroanisole (-2.14 V), and 2,4-dichlorophenoxy- and 2,4,5-trichlorophenoxyacetic acids (-2.35 V and -2.34 V, respectively). The key parameters required to calculate the reduction potential, electron affinity and/or C-Cl bond dissociation energy, were computed at both DFT-D and CCSD(T)-F12 levels. Comparison of the obtained gas-phase energies and redox potentials with experiment enabled us to verify the relative energetics and the performance of various implicit solvent models. Good agreement with the experiment was achieved for redox potentials computed at the DFT-D level, but only for the stepwise mechanism owing to the error compensation. For the concerted electron transfer/C-Cl bond cleavage process, the application of a high level coupled cluster method is required. Quantum chemical calculations have also demonstrated the significant role of the π*ring and σ*C-Cl orbital mixing. It brings about the stabilisation of the non-planar, C2v-symmetric C6Cl6˙(-) radical anion, explains the experimentally observed low energy barrier and the transfer coefficient close to 0.5 for C6Cl5OCH3 in an electron transfer process followed by immediate C-Cl bond cleavage in solution, and an increase in the probability of dechlorination of di- and trichlorophenoxyacetic acids due to substantial population of the vibrational excited states corresponding to the out-of-plane C-Cl bending at ambient temperatures.

  3. Dissociative electron transfer in polychlorinated aromatics. Reduction potentials from convolution analysis and quantum chemical calculations.

    PubMed

    Romańczyk, Piotr P; Rotko, Grzegorz; Kurek, Stefan S

    2016-08-10

    Formal potentials of the first reduction leading to dechlorination in dimethylformamide were obtained from convolution analysis of voltammetric data and confirmed by quantum chemical calculations for a series of polychlorinated benzenes: hexachlorobenzene (-2.02 V vs. Fc(+)/Fc), pentachloroanisole (-2.14 V), and 2,4-dichlorophenoxy- and 2,4,5-trichlorophenoxyacetic acids (-2.35 V and -2.34 V, respectively). The key parameters required to calculate the reduction potential, electron affinity and/or C-Cl bond dissociation energy, were computed at both DFT-D and CCSD(T)-F12 levels. Comparison of the obtained gas-phase energies and redox potentials with experiment enabled us to verify the relative energetics and the performance of various implicit solvent models. Good agreement with the experiment was achieved for redox potentials computed at the DFT-D level, but only for the stepwise mechanism owing to the error compensation. For the concerted electron transfer/C-Cl bond cleavage process, the application of a high level coupled cluster method is required. Quantum chemical calculations have also demonstrated the significant role of the π*ring and σ*C-Cl orbital mixing. It brings about the stabilisation of the non-planar, C2v-symmetric C6Cl6˙(-) radical anion, explains the experimentally observed low energy barrier and the transfer coefficient close to 0.5 for C6Cl5OCH3 in an electron transfer process followed by immediate C-Cl bond cleavage in solution, and an increase in the probability of dechlorination of di- and trichlorophenoxyacetic acids due to substantial population of the vibrational excited states corresponding to the out-of-plane C-Cl bending at ambient temperatures. PMID:27477334

  4. Geothermal Energy: Tapping the Potential

    ERIC Educational Resources Information Center

    Johnson, Bill

    2008-01-01

    Ground source geothermal energy enables one to tap into the earth's stored renewable energy for heating and cooling facilities. Proper application of ground-source geothermal technology can have a dramatic impact on the efficiency and financial performance of building energy utilization (30%+). At the same time, using this alternative energy…

  5. The effect of calculated explosive energy output on blast design

    SciTech Connect

    Katsabanis, P.D.; Workman, L.

    1996-12-31

    The energy output of an explosive is typically calculated using an equation of state and computer applications. Results are reported as weight and bulk strength, either in absolute terms or relative to ANFO. The effect of the equation of state selected and the assumptions regarding the energy calculation are considered and interpreted for the purpose of blast design. It appears that variations in the heat of detonation which result from the selection of the equation of state and parameters associated with it are not sufficient to significantly affect blast patterns, explosive consumption and costs. However variations stemming from the use of available energy associated with a cut-off pressure are significant, suggesting in many cases large pattern expansions. The validity of the various approaches is discussed and blast design results based on the energy calculated by the different approaches are presented and evaluated.

  6. Neutron absorbed dose determination by calculations of recoil energy.

    PubMed

    Wrobel, F; Benabdesselam, M; Iacconi, P; Lapraz, D

    2004-01-01

    The aim of this work is to calculate the absorbed dose to matter due to neutrons in the 5-150 MeV energy range. Materials involved in the calculations are Al2O3, CaSO4 and CaS, which may be used as dosemeters and have already been studied for their luminescent properties. The absorbed dose is assumed to be mainly due to the energy deposited by the recoils. Elastic reactions are treated with the ECIS code while for the non-elastic ones, a Monte Carlo code has been developed and allowed to follow the nucleus decay and to determine its characteristics (nature and energy). Finally, the calculations show that the absorbed dose is mainly due to non-elastic process and that above 20 MeV this dose decreases slightly with the neutron energy. PMID:15353750

  7. Potential of renewable and alternative energy sources

    NASA Astrophysics Data System (ADS)

    Konovalov, V.; Pogharnitskaya, O.; Rostovshchikova, A.; Matveenko, I.

    2015-11-01

    The article deals with application potential of clean alternative renewable energy sources. By means of system analysis the forecast for consumption of electrical energy in Tomsk Oblast as well as main energy sources of existing energy system have been studied up to 2018. Engineering potential of renewable and alternative energy sources is evaluated. Besides, ranking in the order of their efficiency descending is performed. It is concluded that Tomsk Oblast has high potential of alternative and renewable energy sources, among which the most promising development perspective is implementation of gasification stations to save fuel consumed by diesel power stations as well as building wind-power plants.

  8. Performance calculation and simulation system of high energy laser weapon

    NASA Astrophysics Data System (ADS)

    Wang, Pei; Liu, Min; Su, Yu; Zhang, Ke

    2014-12-01

    High energy laser weapons are ready for some of today's most challenging military applications. Based on the analysis of the main tactical/technical index and combating process of high energy laser weapon, a performance calculation and simulation system of high energy laser weapon was established. Firstly, the index decomposition and workflow of high energy laser weapon was proposed. The entire system was composed of six parts, including classical target, platform of laser weapon, detect sensor, tracking and pointing control, laser atmosphere propagation and damage assessment module. Then, the index calculation modules were designed. Finally, anti-missile interception simulation was performed. The system can provide reference and basis for the analysis and evaluation of high energy laser weapon efficiency.

  9. Calculating fusion neutron energy spectra from arbitrary reactant distributions

    NASA Astrophysics Data System (ADS)

    Eriksson, J.; Conroy, S.; Andersson Sundén, E.; Hellesen, C.

    2016-02-01

    The Directional Relativistic Spectrum Simulator (DRESS) code can perform Monte-Carlo calculations of reaction product spectra from arbitrary reactant distributions, using fully relativistic kinematics. The code is set up to calculate energy spectra from neutrons and alpha particles produced in the D(d, n)3He and T(d, n)4He fusion reactions, but any two-body reaction can be simulated by including the corresponding cross section. The code has been thoroughly tested. The kinematics calculations have been benchmarked against the kinematics module of the ROOT Data Analysis Framework. Calculated neutron energy spectra have been validated against tabulated fusion reactivities and against an exact analytical expression for the thermonuclear fusion neutron spectrum, with good agreement. The DRESS code will be used as the core of a detailed synthetic diagnostic framework for neutron measurements at the JET and MAST tokamaks.

  10. Determination of a silane intermolecular force field potential model from an ab initio calculation

    SciTech Connect

    Li, Arvin Huang-Te; Chao, Sheng D.; Chang, Chien-Cheng

    2010-12-15

    Intermolecular interaction potentials of the silane dimer in 12 orientations have been calculated by using the Hartree-Fock (HF) self-consistent theory and the second-order Moeller-Plesset (MP2) perturbation theory. We employed basis sets from Pople's medium-size basis sets [up to 6-311++G(3df, 3pd)] and Dunning's correlation consistent basis sets (up to the triply augmented correlation-consistent polarized valence quadruple-zeta basis set). We found that the minimum energy orientations were the G and H conformers. We have suggested that the Si-H attractions, the central silicon atom size, and electronegativity play essential roles in weakly binding of a silane dimer. The calculated MP2 potential data were employed to parametrize a five-site force field for molecular simulations. The Si-Si, Si-H, and H-H interaction parameters in a pairwise-additive, site-site potential model for silane molecules were regressed from the ab initio energies.

  11. Heavy-ion fission probability calculations at high excitation energy

    SciTech Connect

    D'Arrigo, A.; Giardina, G.; Taccone, A. Istituto Nazionale di Fisica Nucleare, Gruppo Collegato di Messina, Messina Istituto di Tecniche Spettroscopiche del Consiglio Nazionale delle Ricerche, Messina )

    1991-12-01

    In the framework of the statistical theory of nuclear reactions we calculated the fission probability {ital P}{sub {ital f}} of the {sup 153}Tb, {sup 158}Er, {sup 159}Dy, {sup 175}Hf, {sup 179}Ta, {sup 186}Os, and {sup 188}Os nuclei with a mass number {ital A}=150--200 produced by heavy-ion reactions. Starting from the spectra of the single-particle levels as determined by Nix and Moeller, and utilizing a formalism we developed, we determined the excitation energy dependence of the effective level density parameters for the fission and the neutron emission channels. The agreement between the fission probability calculations and the experimental data was reached when a nonadiabatic estimate of the collective effects was used to calculate the nuclear level density. In the fission process at high excitation energies induced by ions heavier than the {alpha} particle, an energy dependence of the effective fission barrier has to be used.

  12. Ab Initio Potential Energy Surface for H-H2

    NASA Technical Reports Server (NTRS)

    Patridge, Harry; Bauschlicher, Charles W., Jr.; Stallcop, James R.; Levin, Eugene

    1993-01-01

    Ab initio calculations employing large basis sets are performed to determine an accurate potential energy surface for H-H2 interactions for a broad range of separation distances. At large distances, the spherically averaged potential determined from the calculated energies agrees well with the corresponding results determined from dispersion coefficients; the van der Waals well depth is predicted to be 75 +/- 3 micro E(h). Large basis sets have also been applied to reexamine the accuracy of theoretical repulsive potential energy surfaces (25-70 kcal/mol above the H-H2 asymptote) at small interatomic separations; the Boothroyd, Keogh, Martin, and Peterson (BKMP) potential energy surface is found to agree with results of the present calculations within the expected uncertainty (+/- 1 kcal/mol) of the fit. Multipolar expansions of the computed H-H2 potential energy surface are reported for four internuclear separation distances (1.2, 1.401, 1.449, and 1.7a(0)) of the hydrogen molecule. The differential elastic scattering cross section calculated from the present results is compared with the measurements from a crossed beam experiment.

  13. Assessment of wind energy potential in Poland

    NASA Astrophysics Data System (ADS)

    Starosta, Katarzyna; Linkowska, Joanna; Mazur, Andrzej

    2014-05-01

    The aim of the presentation is to show the suitability of using numerical model wind speed forecasts for the wind power industry applications in Poland. In accordance with the guidelines of the European Union, the consumption of wind energy in Poland is rapidly increasing. According to the report of Energy Regulatory Office from 30 March 2013, the installed capacity of wind power in Poland was 2807MW from 765 wind power stations. Wind energy is strongly dependent on the meteorological conditions. Based on the climatological wind speed data, potential energy zones within the area of Poland have been developed (H. Lorenc). They are the first criterion for assessing the location of the wind farm. However, for exact monitoring of a given wind farm location the prognostic data from numerical model forecasts are necessary. For the practical interpretation and further post-processing, the verification of the model data is very important. Polish Institute Meteorology and Water Management - National Research Institute (IMWM-NRI) runs an operational model COSMO (Consortium for Small-scale Modelling, version 4.8) using two nested domains at horizontal resolutions of 7 km and 2.8 km. The model produces 36 hour and 78 hour forecasts from 00 UTC, for 2.8 km and 7 km domain resolutions respectively. Numerical forecasts were compared with the observation of 60 SYNOP and 3 TEMP stations in Poland, using VERSUS2 (Unified System Verification Survey 2) and R package. For every zone the set of statistical indices (ME, MAE, RMSE) was calculated. Forecast errors for aerological profiles are shown for Polish TEMP stations at Wrocław, Legionowo and Łeba. The current studies are connected with a topic of the COST ES1002 WIRE-Weather Intelligence for Renewable Energies.

  14. An adaptive interpolation scheme for molecular potential energy surfaces

    NASA Astrophysics Data System (ADS)

    Kowalewski, Markus; Larsson, Elisabeth; Heryudono, Alfa

    2016-08-01

    The calculation of potential energy surfaces for quantum dynamics can be a time consuming task—especially when a high level of theory for the electronic structure calculation is required. We propose an adaptive interpolation algorithm based on polyharmonic splines combined with a partition of unity approach. The adaptive node refinement allows to greatly reduce the number of sample points by employing a local error estimate. The algorithm and its scaling behavior are evaluated for a model function in 2, 3, and 4 dimensions. The developed algorithm allows for a more rapid and reliable interpolation of a potential energy surface within a given accuracy compared to the non-adaptive version.

  15. An adaptive interpolation scheme for molecular potential energy surfaces.

    PubMed

    Kowalewski, Markus; Larsson, Elisabeth; Heryudono, Alfa

    2016-08-28

    The calculation of potential energy surfaces for quantum dynamics can be a time consuming task-especially when a high level of theory for the electronic structure calculation is required. We propose an adaptive interpolation algorithm based on polyharmonic splines combined with a partition of unity approach. The adaptive node refinement allows to greatly reduce the number of sample points by employing a local error estimate. The algorithm and its scaling behavior are evaluated for a model function in 2, 3, and 4 dimensions. The developed algorithm allows for a more rapid and reliable interpolation of a potential energy surface within a given accuracy compared to the non-adaptive version. PMID:27586901

  16. An adaptive interpolation scheme for molecular potential energy surfaces.

    PubMed

    Kowalewski, Markus; Larsson, Elisabeth; Heryudono, Alfa

    2016-08-28

    The calculation of potential energy surfaces for quantum dynamics can be a time consuming task-especially when a high level of theory for the electronic structure calculation is required. We propose an adaptive interpolation algorithm based on polyharmonic splines combined with a partition of unity approach. The adaptive node refinement allows to greatly reduce the number of sample points by employing a local error estimate. The algorithm and its scaling behavior are evaluated for a model function in 2, 3, and 4 dimensions. The developed algorithm allows for a more rapid and reliable interpolation of a potential energy surface within a given accuracy compared to the non-adaptive version.

  17. Exam Question Exchange: Potential Energy Surfaces.

    ERIC Educational Resources Information Center

    Alexander, John J., Ed.

    1988-01-01

    Presents three examination questions, graded in difficulty, that explore the topic of potential energy surfaces using a diagrammatic approach. Provides and discusses acceptable solutions including diagrams. (CW)

  18. Calculation of exchange energies using algebraic perturbation theory

    SciTech Connect

    Burrows, B. L.; Dalgarno, A.; Cohen, M.

    2010-04-15

    An algebraic perturbation theory is presented for efficient calculations of localized states and hence of exchange energies, which are the differences between low-lying states of the valence electron of a molecule, formed by the collision of an ion Y{sup +} with an atom X. For the case of a homonuclear molecule these are the gerade and ungerade states and the exchange energy is an exponentially decreasing function of the internuclear distance. For such homonuclear systems the theory is used in conjunction with the Herring-Holstein technique to give accurate exchange energies for a range of intermolecular separations R. Since the perturbation parameter is essentially 1/R, this method is suitable for large R. In particular, exchange energies are calculated for X{sub 2}{sup +} systems, where X is H, Li, Na, K, Rb, or Cs.

  19. Calculating Ring Pucker Free Energy Surfaces From Reaction Coordinate Forces

    SciTech Connect

    Barnett, Christopher B.; Naidoo, Kevin J.

    2009-03-09

    We implemented the free energy from adaptive reaction coordinate forces (FEARCF) method and applied it to the conformational investigation of carbohydrate ring puckering. The method allows for significantly enhanced sampling of reaction coordinate space. The free energies associated with the ring pucker motion of {beta}-D-ribose (a furanose) and {beta}-D-glucose (a pyranose) were calculated. These can be used to interpret catalytic mechanisms of glycosylases.

  20. Removing the barrier to the calculation of activation energies

    NASA Astrophysics Data System (ADS)

    Mesele, Oluwaseun O.; Thompson, Ward H.

    2016-10-01

    Approaches for directly calculating the activation energy for a chemical reaction from a simulation at a single temperature are explored with applications to both classical and quantum systems. The activation energy is obtained from a time correlation function that can be evaluated from the same molecular dynamics trajectories or quantum dynamics used to evaluate the rate constant itself and thus requires essentially no extra computational work.

  1. Potential theoretic methods for far field sound radiation calculations

    NASA Technical Reports Server (NTRS)

    Hariharan, S. I.; Stenger, Edward J.; Scott, J. R.

    1995-01-01

    In the area of computational acoustics, procedures which accurately predict the far-field sound radiation are much sought after. A systematic development of such procedures are found in a sequence of papers by Atassi. The method presented here is an alternate approach to predicting far field sound based on simple layer potential theoretic methods. The main advantages of this method are: it requires only a simple free space Green's function, it can accommodate arbitrary shapes of Kirchoff surfaces, and is readily extendable to three-dimensional problems. Moreover, the procedure presented here, though tested for unsteady lifting airfoil problems, can easily be adapted to other areas of interest, such as jet noise radiation problems. Results are presented for lifting airfoil problems and comparisons are made with the results reported by Atassi. Direct comparisons are also made for the flat plate case.

  2. Semi-infinite jellium: Thermodynamic potential, chemical potential, and surface energy

    NASA Astrophysics Data System (ADS)

    Kostrobij, P. P.; Markovych, B. M.

    2015-08-01

    A general expression for the thermodynamic potential of the model of semi-infinite jellium is obtained. By using this expression, the surface energy for the infinite barrier model is calculated. The behavior of the surface energy and of the chemical potential as functions of the Wigner-Seitz radius and the influence of the Coulomb interaction between electrons on the calculated values is studied. It is shown that taking into account the Coulomb interaction between electrons leads to growth of the surface energy. The surface energy is positive in the entire area of the Wigner-Seitz radius. It is shown that taking into account the Coulomb interaction between electrons leads to a decrease of the chemical potential.

  3. Periodic discrete energy for long-range potentials

    NASA Astrophysics Data System (ADS)

    Hardin, D. P.; Saff, E. B.; Simanek, B.

    2014-12-01

    We consider periodic energy problems in Euclidean space with a special emphasis on long-range potentials that cannot be defined through the usual infinite sum. One of our main results builds on more recent developments of Ewald summation to define the periodic energy corresponding to a large class of long-range potentials. Two particularly interesting examples are the logarithmic potential and the Riesz potential when the Riesz parameter is smaller than the dimension of the space. For these examples, we use analytic continuation methods to provide concise formulas for the periodic kernel in terms of the Epstein Hurwitz Zeta function. We apply our energy definition to deduce several properties of the minimal energy including the asymptotic order of growth and the distribution of points in energy minimizing configurations as the number of points becomes large. We conclude with some detailed calculations in the case of one dimension, which shows the utility of this approach.

  4. General method for calculating derivatives of the lattice electrostatic energy.

    NASA Technical Reports Server (NTRS)

    Macdonald, D. E.; Eftis, J.; Arkilic, G. M.

    1972-01-01

    A method for calculating the derivatives of lattice electrostatic strain energy is proposed. It offers a computation procedure that is more general, concise, and systematic than any of the procedures previously used by Fuchs (1936), Cousins (1967), and Suzuki et al. (1968). The method can also easily be extended to fourth- and higher-order derivatives without undue difficulty.

  5. Contrastive studies of potential energy functions of some diatomic molecules

    NASA Astrophysics Data System (ADS)

    Abdallah, Hassan H.; Abdullah, Hewa Y.

    2016-03-01

    It was proposed that iron hydride, FeH, would be formed only on grains at the clouds through the reaction of the adsorbed H atoms or H2 molecules with the adsorbed Fe atoms on the grains. The importance of FeH in Astrophysics presents an additional motivation to study its energetic, spectroscopic constants and Potential Energy Curves. The structural optimization for ground state of FeH was calculated by different theoretical methods, namely, Hartree-Fock (HF), the density functional theory (DFT), B3LYP, MP2 method and QCISD(T) methods and compared with available data from the literature. The single ionized forms, cation and anion, were also obtained at the same level of calculations. Charges, dipole moment, geometrical parameters, molecular orbital energies and spectroscopic parameters were calculated and reported. In addition, the molecular ionization potential, electron affinity and dissociation energy were investigated.

  6. Electronic coupling calculations with transition charges, dipoles, and quadrupoles derived from electrostatic potential fitting

    SciTech Connect

    Fujimoto, Kazuhiro J.

    2014-12-07

    A transition charge, dipole, and quadrupole from electrostatic potential (TrESP-CDQ) method for electronic coupling calculations is proposed. The TrESP method is based on the classical description of electronic Coulomb interaction between transition densities for individual molecules. In the original TrESP method, only the transition charge interactions were considered as the electronic coupling. In the present study, the TrESP method is extended to include the contributions from the transition dipoles and quadrupoles as well as the transition charges. Hence, the self-consistent transition density is employed in the ESP fitting procedure. To check the accuracy of the present approach, several test calculations are performed to a helium dimer, a methane dimer, and an ethylene dimer. As a result, the TrESP-CDQ method gives a much improved description of the electronic coupling, compared with the original TrESP method. The calculated results also show that the self-consistent treatment to the transition densities contributes significantly to the accuracy of the electronic coupling calculations. Based on the successful description of the electronic coupling, the contributions to the electronic coupling are also analyzed. This analysis clearly shows a negligible contribution of the transition charge interaction to the electronic coupling. Hence, the distribution of the transition density is found to strongly influence the magnitudes of the transition charges, dipoles, and quadrupoles. The present approach is useful for analyzing and understanding the mechanism of excitation-energy transfer.

  7. Accurate calculation of diffraction-limited encircled and ensquared energy.

    PubMed

    Andersen, Torben B

    2015-09-01

    Mathematical properties of the encircled and ensquared energy functions for the diffraction-limited point-spread function (PSF) are presented. These include power series and a set of linear differential equations that facilitate the accurate calculation of these functions. Asymptotic expressions are derived that provide very accurate estimates for the relative amount of energy in the diffraction PSF that fall outside a square or rectangular large detector. Tables with accurate values of the encircled and ensquared energy functions are also presented. PMID:26368873

  8. Calculation of Mg(+)-ligand relative binding energies

    NASA Technical Reports Server (NTRS)

    Partridge, Harry; Bauschlicher, Charles W., Jr.

    1992-01-01

    The calculated relative binding energies of 16 organic molecules to Mg(+) are compared with experimental results where available. The geometries of the ligands and the Mg(+)-ligand complexes arc optimized at the self-consistent field level using a 6-31G* basis set. The Mg(+) binding energies are evaluated using second-order perturbation theory and basis sets of triple-sigma quality augmented with two sets of polarization functions. This level of theory is calibrated against higher levels of theory for selected systems. The computed binding energies are accurate to about 2 kcal/mol.

  9. The Calculation of Accurate Metal-Ligand Bond Energies

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W.; Partridge, Harry, III; Ricca, Alessandra; Arnold, James O. (Technical Monitor)

    1997-01-01

    The optimization of the geometry and calculation of zero-point energies are carried out at the B3LYP level of theory. The bond energies are determined at this level, as well as at the CCSD(T) level using very large basis sets. The successive OH bond energies to the first row transition metal cations are reported. For most systems there has been an experimental determination of the first OH. In general, the CCSD(T) values are in good agreement with experiment. The bonding changes from mostly covalent for the early metals to mostly electrostatic for the late transition metal systems.

  10. Potential Water and Energy Savings from Showerheads

    SciTech Connect

    Biermayer, Peter J.

    2005-09-28

    This paper estimates the benefits and costs of six water reduction scenarios. Benefits and costs of showerhead scenarios are ranked in this paper by an estimated water reduction percentage. To prioritize potential water and energy saving scenarios regarding showerheads, six scenarios were analyzed for their potential water and energy savings and the associated dollar savings to the consumer.

  11. Ab initio calculation of thermodynamic potentials and entropies for superionic water

    DOE PAGES

    French, Martin; Desjarlais, Michael P.; Redmer, Ronald

    2016-02-25

    We construct thermodynamic potentials for two superionic phases of water [with body-centered cubic (bcc) and face-centered cubic (fcc) oxygen lattice] using a combination of density functional theory (DFT) and molecular dynamics simulations (MD). For this purpose, a generic expression for the free energy of warm dense matter is developed and parametrized with equation of state data from the DFT-MD simulations. A second central aspect is the accurate determination of the entropy, which is done using an approximate two-phase method based on the frequency spectra of the nuclear motion. The boundary between the bcc superionic phase and the ices VII andmore » X calculated with thermodynamic potentials from DFT-MD is consistent with that directly derived from the simulations. As a result, differences in the physical properties of the bcc and fcc superionic phases and their impact on interior modeling of water-rich giant planets are discussed.« less

  12. Ab initio calculation of thermodynamic potentials and entropies for superionic water.

    PubMed

    French, Martin; Desjarlais, Michael P; Redmer, Ronald

    2016-02-01

    We construct thermodynamic potentials for two superionic phases of water [with body-centered cubic (bcc) and face-centered cubic (fcc) oxygen lattice] using a combination of density functional theory (DFT) and molecular dynamics simulations (MD). For this purpose, a generic expression for the free energy of warm dense matter is developed and parametrized with equation of state data from the DFT-MD simulations. A second central aspect is the accurate determination of the entropy, which is done using an approximate two-phase method based on the frequency spectra of the nuclear motion. The boundary between the bcc superionic phase and the ices VII and X calculated with thermodynamic potentials from DFT-MD is consistent with that directly derived from the simulations. Differences in the physical properties of the bcc and fcc superionic phases and their impact on interior modeling of water-rich giant planets are discussed. PMID:26986321

  13. Ab initio calculation of thermodynamic potentials and entropies for superionic water

    NASA Astrophysics Data System (ADS)

    French, Martin; Desjarlais, Michael P.; Redmer, Ronald

    2016-02-01

    We construct thermodynamic potentials for two superionic phases of water [with body-centered cubic (bcc) and face-centered cubic (fcc) oxygen lattice] using a combination of density functional theory (DFT) and molecular dynamics simulations (MD). For this purpose, a generic expression for the free energy of warm dense matter is developed and parametrized with equation of state data from the DFT-MD simulations. A second central aspect is the accurate determination of the entropy, which is done using an approximate two-phase method based on the frequency spectra of the nuclear motion. The boundary between the bcc superionic phase and the ices VII and X calculated with thermodynamic potentials from DFT-MD is consistent with that directly derived from the simulations. Differences in the physical properties of the bcc and fcc superionic phases and their impact on interior modeling of water-rich giant planets are discussed.

  14. Three dimensional calculation of flux of low energy atmospheric neutrinos

    NASA Technical Reports Server (NTRS)

    Lee, H.; Bludman, S. A.

    1985-01-01

    Results of three-dimensional Monte Carlo calculation of low energy flux of atmospheric neutrinos are presented and compared with earlier one-dimensional calculations 1,2 valid at higher neutrino energies. These low energy neutrinos are the atmospheric background in searching for neutrinos from astrophysical sources. Primary cosmic rays produce the neutrino flux peaking at near E sub=40 MeV and neutrino intensity peaking near E sub v=100 MeV. Because such neutrinos typically deviate by 20 approximately 30 from the primary cosmic ray direction, three-dimensional effects are important for the search of atmospheric neutrinos. Nevertheless, the background of these atmospheric neutrinos is negligible for the detection of solar and supernova neutrinos.

  15. Calculation of energy for lighting using EN 15193

    NASA Astrophysics Data System (ADS)

    Mitsopoulou, Mairi

    The aim of this report is to investigate the impact of the application of the new European directive prEN 15193, concerning the Energy performance of buildings - Energy requirements for lighting on the design of artificial lighting in open plan office buildings. A study of the energy consequences of three different types of building and different types of lighting systems within the buildings was carried out. The result of the study helped understand how each type of building performs in terms of the amount of energy that is used in the lighting the study also helped to verify the calculation procedure LENI used in EN 15193 Energy Performance of Buildings - Energy Requirements for Lighting. The efficient use of energy for lighting can reduce operating costs by reducing the energy consumption for lighting. Besides direct savings, indirect energy savings can be found in buildings, with high cooling loads because of the reduced heat production and thus, the reduced energy consumption for air conditioning, a fact that in a worldwide scale will have important environmental benefits.

  16. Geothermal Energy Potential in Western United States

    ERIC Educational Resources Information Center

    Pryde, Philip R.

    1977-01-01

    Reviews types of geothermal energy sources in the western states, including hot brine systems and dry steam systems. Conversion to electrical energy is a major potential use of geothermal energy, although it creates environmental disruptions such as noise, corrosion, and scaling of equipment. (AV)

  17. Composite electron propagator methods for calculating ionization energies

    NASA Astrophysics Data System (ADS)

    Díaz-Tinoco, Manuel; Dolgounitcheva, O.; Zakrzewski, V. G.; Ortiz, J. V.

    2016-06-01

    Accurate ionization energies of molecules may be determined efficiently with composite electron-propagator (CEP) techniques. These methods estimate the results of a calculation with an advanced correlation method and a large basis set by performing a series of more tractable calculations in which large basis sets are used with simpler approximations and small basis sets are paired with more demanding correlation techniques. The performance of several CEP methods, in which diagonal, second-order electron propagator results with large basis sets are combined with higher-order results obtained with smaller basis sets, has been tested for the ionization energies of closed-shell molecules from the G2 set. Useful compromises of accuracy and computational efficiency employ complete-basis-set extrapolation for second-order results and small basis sets in third-order, partial third-order, renormalized partial-third order, or outer valence Green's function calculations. Analysis of results for vertical as well as adiabatic ionization energies leads to specific recommendations on the best use of regular and composite methods. Results for 22 organic molecules of interest in the design of photovoltaic devices, benzo[a]pyrene, Mg-octaethylporphyrin, and C60 illustrate the capabilities of CEP methods for calculations on large molecules.

  18. Composite electron propagator methods for calculating ionization energies.

    PubMed

    Díaz-Tinoco, Manuel; Dolgounitcheva, O; Zakrzewski, V G; Ortiz, J V

    2016-06-14

    Accurate ionization energies of molecules may be determined efficiently with composite electron-propagator (CEP) techniques. These methods estimate the results of a calculation with an advanced correlation method and a large basis set by performing a series of more tractable calculations in which large basis sets are used with simpler approximations and small basis sets are paired with more demanding correlation techniques. The performance of several CEP methods, in which diagonal, second-order electron propagator results with large basis sets are combined with higher-order results obtained with smaller basis sets, has been tested for the ionization energies of closed-shell molecules from the G2 set. Useful compromises of accuracy and computational efficiency employ complete-basis-set extrapolation for second-order results and small basis sets in third-order, partial third-order, renormalized partial-third order, or outer valence Green's function calculations. Analysis of results for vertical as well as adiabatic ionization energies leads to specific recommendations on the best use of regular and composite methods. Results for 22 organic molecules of interest in the design of photovoltaic devices, benzo[a]pyrene, Mg-octaethylporphyrin, and C60 illustrate the capabilities of CEP methods for calculations on large molecules. PMID:27305999

  19. Energy potential of modern landfills

    SciTech Connect

    Bogner, J.E.

    1990-01-01

    Methane produced by refuse decomposition in a sanitary landfill can be recovered for commercial use. Landfill methane is currently under-utilized, with commercial recovery at only a small percentage of US landfills. New federal regulations mandating control of landfill gas migration and atmospheric emissions are providing impetus to methane recovery schemes as a means of recovering costs for increased environmental control. The benefits of landfill methane recovery include utilization of an inexpensive renewable energy resource, removal of explosive gas mixtures from the subsurface, and mitigation of observed historic increases in atmospheric methane. Increased commercial interest in landfill methane recovery is dependent on the final form of Clean Air Act amendments pertaining to gaseous emissions from landfills; market shifts in natural gas prices; financial incentives for development of renewable energy resources; and support for applied research and development to develop techniques for increased control of the gas generation process in situ. This paper will discuss the controls on methane generation in landfills. In addition, it will address how landfill regulations affect landfill design and site management practices which, in turn, influence decomposition rates. Finally, future trends in landfilling, and their relationship to gas production, will be examined. 19 refs., 2 figs., 3 tabs.

  20. New method for calculating binding energies in quantum mechanics and quantum field theories

    SciTech Connect

    Gat, G.; Rosenstein, B. Institute of Physics, Academia Sinica, Taipei, 11529 )

    1993-01-04

    We propose a systematic perturbative method for calculating the binding energy of threshold bound states---states which exist for arbitrary small coupling. The starting point is a (regularized) free theory. Explicit calculations are performed for quantum mechanics with arbitrary short-range potential in 1D and various (1+1)-dimensional quantum field theories. We check the method by comparing the results with exact formulas available in solvable models.

  1. Collisionless Plasma Modeling in an Arbitrary Potential Energy Distribution

    NASA Technical Reports Server (NTRS)

    Liemohn, M. W.; Khazanov, G. V.

    1997-01-01

    A new technique for calculating a collisionless plasma along a field line is presented. The primary feature of the new model is that it can handle an arbitrary (including nonmonotonic) potential energy distribution. This was one of the limiting constraints on the existing models in this class, and these constraints are generalized for an arbitrary potential energy composition. The formulation for relating current density to the field-aligned potential as well as formulas for density, temperature and energy flux calculations are presented for several distribution functions, ranging from a bi-Lorentzian with a loss cone to an isotropic Maxwellian. A comparison of these results with previous models shows that the formulation reduces.to the earlier models under similar assumptions.

  2. Binding Energy Calculations for Novel Ternary Ionic Lattices

    NASA Astrophysics Data System (ADS)

    Rodríguez-Mijangos, Ricardo; Vazquez-Polo, Gustavo

    2002-03-01

    Theoretical calculations for the binding energy between metalic ions and negative ions on a novel ternary ionic lattice is carried out for several solid solutions prepared with different concentrations and characterized recently (1). The ternary lattices that reach a good miscibility are: KCl(x)KBr(y)RbCl(z) in three different concentrations: (x=y=z=0.33), (x=0.5, y=0.25, z=0.25) and (x=0.33, y=0.07, z=0.60). The binding energy for these novel structures is calculated from the lattice constants obtained by X ray diffractometry analysis performed on the samples and the Vegard law (2). For the repulsive force exponent m, an average of the m values was considered. The energy values obtained by the Born´expression are compared with corresponding energy values from the lattice with more complex expressions, such as the Born Mayer, Born-Van der Walls. There is a good aggreement between all these calculations. (1)R. R. Mijangos, A. Cordero-Borboa, E. Alvarez, M. Cervantes, Physics Letters A 282 (2001) 195-200. (2) G. Vazquez-Polo, R. R. Mijangos et al. Revista Mexicana de Fisica, 47, Diciembre 2001. In Press.

  3. Potential energy stored by planets and grand minima events

    NASA Astrophysics Data System (ADS)

    Cionco, Rodolfo G.

    2012-07-01

    Recently, Wolff & Patrone (2010), have developed a simple but very interesting model by which the movement of the Sun around the barycentre of the Solar system could create potential energy that could be released by flows pre-existing inside the Sun. The authors claim that it is the first mechanism showing how planetary movements can modify internal structure in the Sun that can be related to solar cycle. In this work we point out limitations of mentioned mechanism (which is based on interchange arguments), which could be inapplicable to a real star. Then, we calculate the temporal evolution of potential energy stored in zones of Sun's interior in which the potential energy could be most efficiently stored taking into account detailed barycentric Sun dynamics. We show strong variations of potential energy related to Maunder Minimum, Dalton Minimum and the maximum of Cycle 22, around 1990. We discuss briefly possible implications of this putative mechanism to solar cycle specially Grand Minima events.

  4. PDB ligand conformational energies calculated quantum-mechanically.

    PubMed

    Sitzmann, Markus; Weidlich, Iwona E; Filippov, Igor V; Liao, Chenzhong; Peach, Megan L; Ihlenfeldt, Wolf-Dietrich; Karki, Rajeshri G; Borodina, Yulia V; Cachau, Raul E; Nicklaus, Marc C

    2012-03-26

    We present here a greatly updated version of an earlier study on the conformational energies of protein-ligand complexes in the Protein Data Bank (PDB) [Nicklaus et al. Bioorg. Med. Chem. 1995, 3, 411-428], with the goal of improving on all possible aspects such as number and selection of ligand instances, energy calculations performed, and additional analyses conducted. Starting from about 357,000 ligand instances deposited in the 2008 version of the Ligand Expo database of the experimental 3D coordinates of all small-molecule instances in the PDB, we created a "high-quality" subset of ligand instances by various filtering steps including application of crystallographic quality criteria and structural unambiguousness. Submission of 640 Gaussian 03 jobs yielded a set of about 415 successfully concluded runs. We used a stepwise optimization of internal degrees of freedom at the DFT level of theory with the B3LYP/6-31G(d) basis set and a single-point energy calculation at B3LYP/6-311++G(3df,2p) after each round of (partial) optimization to separate energy changes due to bond length stretches vs bond angle changes vs torsion changes. Even for the most "conservative" choice of all the possible conformational energies-the energy difference between the conformation in which all internal degrees of freedom except torsions have been optimized and the fully optimized conformer-significant energy values were found. The range of 0 to ~25 kcal/mol was populated quite evenly and independently of the crystallographic resolution. A smaller number of "outliers" of yet higher energies were seen only at resolutions above 1.3 Å. The energies showed some correlation with molecular size and flexibility but not with crystallographic quality metrics such as the Cruickshank diffraction-component precision index (DPI) and R(free)-R, or with the ligand instance-specific metrics such as occupancy-weighted B-factor (OWAB), real-space R factor (RSR), and real-space correlation coefficient

  5. Perspective on Free-Energy Perturbation Calculations for Chemical Equilibria

    PubMed Central

    Jorgensen, William L.; Thomas, Laura L.

    2009-01-01

    An overview is provided on the computation of free energy changes in solution using perturbation theory, overlap sampling, and related approximate methods. As a specific application, extensive results are provided for free energies of hydration of substituted benzenes using the OPLS-AA force field in explicit TIP4P water. For a similar amount of computer time, the double-wide sampling and overlap sampling methods yield very similar results in the free-energy perturbation calculations. With standard protocols, the average statistical uncertainty in computed differences in free energies of hydration is 0.1 – 0.2 kcal/mol. Application of the power-series expansion in the Peierls equation was also tested. Use of the first-order term is generally reliable, while inclusion of the slowly-convergent, second-order fluctuation term causes deterioration in the results for strongly hydrogen-bonded solutes. PMID:19936324

  6. Self-consistent calculations of alpha-decay energies

    SciTech Connect

    Tolokonnikov, S. V.; Lutostansky, Yu. S.; Saperstein, E. E.

    2013-06-15

    On the basis of the self-consistent theory of finite Fermi systems, the energies of alphadecay chains were calculated for several new superheavy nuclei discovered recently in experiments of the Dubna-Livermore Collaboration headed by Yu.Ts. Oganessian. The approach in question is implemented on the basis of the generalized method of the density functional proposed by Fayans and his coauthors. The version used here relies on the functional DF3-a proposed recently for describing a wide array of nuclear data, including data on superheavy nuclei. A detailed comparison of the results obtained on this basis with the predictions of different approaches, including the self-consistent Skyrme-Hartree-Fock method, the micro-macro method in the version developed by Sobiczewski and his coauthors, and the phenomenological method of Liran and his coauthors, is performed. The resulting alpha-decay energies are used to calculate respective lifetimes with the aid of the phenomenological Parkhomenko-Sobiczewski formula.

  7. Ab Initio Calculations for the Surface Energy of Silver Nanoclusters

    NASA Astrophysics Data System (ADS)

    Medasani, Bharat; Vasiliev, Igor; Park, Young Ho

    2007-03-01

    We apply first principles computational methods to study the surface energy and the surface stress of silver nanoparticles. The structures, energies and lattice contractions of spherical Ag nanoclusters are calculated in the framework of density functional theory combined with the generalized gradient approximation. Our calculations predict the surface energies of Ag nanoclusters to be in the range of 1-2 J/m^2. These values are close to the bulk surface energy of silver, but are significantly lower than the recently reported value of 7.2 J/m^2 derived from the Kelvin equation for free Ag nanoparticles. From the lattice contraction and the nearest neighbor interatomic distance, we estimate the surface stress of the silver nanoclusters to be in the the range of 1-1.45 N/m. This result suggests that a liquid droplet model can be employed to evaluate the surface energy and the surface stress of Ag nanoparticles. K. K. Nanda et al., Phys. Rev. Lett. 91, 106102 (2003).

  8. Calculating Free Energies Using Scaled-Force Molecular Dynamics Algorithm

    NASA Technical Reports Server (NTRS)

    Darve, Eric; Wilson, Micahel A.; Pohorille, Andrew

    2000-01-01

    One common objective of molecular simulations in chemistry and biology is to calculate the free energy difference between different states of the system of interest. Examples of problems that have such an objective are calculations of receptor-ligand or protein-drug interactions, associations of molecules in response to hydrophobic, and electrostatic interactions or partition of molecules between immiscible liquids. Another common objective is to describe evolution of the system towards a low energy (possibly the global minimum energy), 'native' state. Perhaps the best example of such a problem is folding of proteins or short RNA molecules. Both types of problems share the same difficulty. Often, different states of the system are separated by high energy barriers, which implies that transitions between these states are rare events. This, in turn, can greatly impede exploration of phase space. In some instances this can lead to 'quasi non-ergodicity', whereby a part of phase space is inaccessible on timescales of the simulation. A host of strategies has been developed to improve efficiency of sampling the phase space. For example, some Monte Carlo techniques involve large steps which move the system between low-energy regions in phase space without the need for sampling the configurations corresponding to energy barriers (J-walking). Most strategies, however, rely on modifying probabilities of sampling low and high-energy regions in phase space such that transitions between states of interest are encouraged. Perhaps the simplest implementation of this strategy is to increase the temperature of the system. This approach was successfully used to identify denaturation pathways in several proteins, but it is clearly not applicable to protein folding. It is also not a successful method for determining free energy differences. Finally, the approach is likely to fail for systems with co-existing phases, such as water-membrane systems, because it may lead to spontaneous

  9. Saint Paul Energy Park: the potential for district heating

    SciTech Connect

    Lee, C.; Kron, R.; Davis, H.

    1980-03-01

    The results of ANL's study of the energy and economic aspects of using district heating in the St. Paul Energy Park are summarized. The Energy Park is a 6 million ft/sup 2/ residential, commercial office, and light industrial complex to be built in the midway area of St. Paul, Minnesota. Space heating and cooling design loads for the park were calculated assuming that the ASHRAE's 90-75 energy-conserving construction standards would be used in constructing the park's buildings. Based in part on this assumption, ANL estimated the costs and energy use characteristics of six possible energy system options for supplying Energy Park's space heating, space cooling, and domestic hot water heating needs. The results indicate that in today's economy, a central heating and cooling plant with natural gas boilers and electrically driven centrifugal chillers with thermal storage has good potential for energy and economic savings and clearly merits further consideration.

  10. Free energy calculations for a flexible water model.

    PubMed

    Habershon, Scott; Manolopoulos, David E

    2011-11-28

    In this work, we consider the problem of calculating the classical free energies of liquids and solids for molecular models with intramolecular flexibility. We show that thermodynamic integration from the fully-interacting solid of interest to a Debye crystal reference state, with anisotropic harmonic interactions derived from the Hessian of the original crystal, provides a straightforward route to calculating the Gibbs free energy of the solid. To calculate the molecular liquid free energy, it is essential to correctly account for contributions from both intermolecular and intramolecular motion; we employ thermodynamic integration to a Lennard-Jones reference fluid, coupled with direct evaluation of the molecular ro-vibrational partition function. These approaches are used to study the low-pressure classical phase diagram of the flexible q-TIP4P/F water model. We find that, while the experimental ice-I/liquid and ice-III/liquid coexistence lines are described reasonably well by this model, the ice-II phase is predicted to be metastable. In light of this finding, we go on to examine how the coupling between intramolecular flexibility and intermolecular interactions influences the computed phase diagram by comparing our results with those of the underlying rigid-body water model. PMID:21887423

  11. Free energy calculations for a flexible water model.

    PubMed

    Habershon, Scott; Manolopoulos, David E

    2011-11-28

    In this work, we consider the problem of calculating the classical free energies of liquids and solids for molecular models with intramolecular flexibility. We show that thermodynamic integration from the fully-interacting solid of interest to a Debye crystal reference state, with anisotropic harmonic interactions derived from the Hessian of the original crystal, provides a straightforward route to calculating the Gibbs free energy of the solid. To calculate the molecular liquid free energy, it is essential to correctly account for contributions from both intermolecular and intramolecular motion; we employ thermodynamic integration to a Lennard-Jones reference fluid, coupled with direct evaluation of the molecular ro-vibrational partition function. These approaches are used to study the low-pressure classical phase diagram of the flexible q-TIP4P/F water model. We find that, while the experimental ice-I/liquid and ice-III/liquid coexistence lines are described reasonably well by this model, the ice-II phase is predicted to be metastable. In light of this finding, we go on to examine how the coupling between intramolecular flexibility and intermolecular interactions influences the computed phase diagram by comparing our results with those of the underlying rigid-body water model.

  12. Free energy perturbation calculations on glucosidase-inhibitor complexes.

    PubMed

    Ruiza, F M; Grigera, J Raúl

    2005-09-01

    Free energy perturbation studies have been performed on Glucoamylase II (471) from Aspergillus awamori var. X100 complexed with three different inhibitors: (+)lentiginosine, (+)(1S,2S,7R,8aS) 1,2,7-trihydroxyindolizidine, (+)(1S,2S,7S,8aS) 1,2,7-trihydroxyindolizidine and the inactive compound (+)(1S,7R,8aS)-1,7-dihydroxyindolizidine. Molecular dynamic simulations were carried out using a recently developed procedure for fast Free Energy Perturbation calculations. In this procedure only a sphere of 1.8 nm around the central atom of the inhibitor is considered in the calculations. Crystallographic restraints are applied over this reduced system using a generated electron density map. The obtained values for the free energy differences agree with experimental data showing the importance of fast calculations in drug design even when the crystallographic structure of the complex is not available. As the method uses only the crystallographic structure of the receptor, it is possible to test the possible efficiency of even still not synthesised ligands, making the pre-selection of compounds much easy and faster.

  13. Sensitivity of methods for calculating energy expenditure by use of doubly labeled water.

    PubMed

    Seale, J; Miles, C; Bodwell, C E

    1989-02-01

    Attempts to estimate human energy expenditure by use of doubly labeled water have produced three methods currently used for calculating carbon dioxide production from isotope disappearance data: 1) the two-point method, 2) the regression method, and 3) the integration method. An ideal data set was used to determine the error produced in the calculated energy expenditure for each method when specific variables were perturbed. The analysis indicates that some of the calculation methods are more susceptible to perturbations in certain variables than others. Results from an experiment on one adult human subject are used to illustrate the potential for error in actual data. Samples of second void urine, 24-h urine, and breath collected every other day for 21 days are used to calculate the average daily energy expenditure by three calculation methods. The difference between calculated energy expenditure and metabolizable energy on a weight-maintenance diet is used to estimate the error associated with the doubly labeled water method. PMID:2496076

  14. Basic ingredients of free energy calculations: a review.

    PubMed

    Christ, Clara D; Mark, Alan E; van Gunsteren, Wilfred F

    2010-06-01

    Methods to compute free energy differences between different states of a molecular system are reviewed with the aim of identifying their basic ingredients and their utility when applied in practice to biomolecular systems. A free energy calculation is comprised of three basic components: (i) a suitable model or Hamiltonian, (ii) a sampling protocol with which one can generate a representative ensemble of molecular configurations, and (iii) an estimator of the free energy difference itself. Alternative sampling protocols can be distinguished according to whether one or more states are to be sampled. In cases where only a single state is considered, six alternative techniques could be distinguished: (i) changing the dynamics, (ii) deforming the energy surface, (iii) extending the dimensionality, (iv) perturbing the forces, (v) reducing the number of degrees of freedom, and (vi) multi-copy approaches. In cases where multiple states are to be sampled, the three primary techniques are staging, importance sampling, and adiabatic decoupling. Estimators of the free energy can be classified as global methods that either count the number of times a given state is sampled or use energy differences. Or, they can be classified as local methods that either make use of the force or are based on transition probabilities. Finally, this overview of the available techniques and how they can be best used in a practical context is aimed at helping the reader choose the most appropriate combination of approaches for the biomolecular system, Hamiltonian and free energy difference of interest.

  15. Free energy calculation of permeation through aquaporin-5

    NASA Astrophysics Data System (ADS)

    Bastien, David

    The work of this paper continues upon the large area of research being done on aquaporins (AQPs). AQPs are proteins that take on the role of facilitating the transfer of substances, mainly water, across cell membranes. There are many different types of AQPs, with each of these highly selective proteins conducting only certain solutes, along with unique permeability rates. The permeation characteristics of aquaporins rely mostly on the residue hydrophobicity and steric restraints of the aromatic arginine (ar/R) region of the protein channel. The purpose of this paper is to analyze the structures of aquaporin-5 (AQP5) and aquaglycerolporin (Glpf), including a radius profile of the respective protein channels, and to compare them to permeation events using steered molecular dynamics (SMD) pulling simulations. Two in silico experiments are performed in order to achieve the free Energy landscape of a single water molecule permeating through the four channels of both Aqp5 and GlpF. The equilibrium free energy curves are calculated from the non-equilibrium, irreversible work measurements using the fluctuation-dissipation theorem (FDT) of Brownian dynamicis (BD). The free energy profiles are then compared and related to the structural profiles of AQP5 and GlpF. The change in free energy across the ar/R region in AQP5 is found to be reasonably larger than that of GlpF. The free energy profiles of AQP5 and GlpF agree with the diameter profile of the channels respectively. Furthermore, free energy calculations are computed for the permeation of Na+ and Cl- ions through the central pore of Aqp5, which provide some insight into the structural mechanisms of AQP5. The free energy barrier for ion transport through the central pore is found to be very large, peaking at around 11 Kcal/mol for chloride and 20 Kcal/mol for sodium.

  16. Investigating energy-saving potentials in the cloud.

    PubMed

    Lee, Da-Sheng

    2014-01-01

    Collecting webpage messages can serve as a sensor for investigating the energy-saving potential of buildings. Focusing on stores, a cloud sensor system is developed to collect data and determine their energy-saving potential. The owner of a store under investigation must register online, report the store address, area, and the customer ID number on the electric meter. The cloud sensor system automatically surveys the energy usage records by connecting to the power company website and calculating the energy use index (EUI) of the store. Other data includes the chain store check, company capital, location price, and the influence of weather conditions on the store; even the exposure frequency of store under investigation may impact the energy usage collected online. After collecting data from numerous stores, a multi-dimensional data array is constructed to determine energy-saving potential by identifying stores with similarity conditions. Similarity conditions refer to analyzed results that indicate that two stores have similar capital, business scale, weather conditions, and exposure frequency on web. Calculating the EUI difference or pure technical efficiency of stores, the energy-saving potential is determined. In this study, a real case study is performed. An 8-dimensional (8D) data array is constructed by surveying web data related to 67 stores. Then, this study investigated the savings potential of the 33 stores, using a site visit, and employed the cloud sensor system to determine the saving potential. The case study results show good agreement between the data obtained by the site visit and the cloud investigation, with errors within 4.17%. Among 33 the samples, eight stores have low saving potentials of less than 5%. The developed sensor on the cloud successfully identifies them as having low saving potential and avoids wasting money on the site visit. PMID:24561405

  17. Pseudospectral Gaussian quantum dynamics: Efficient sampling of potential energy surfaces

    NASA Astrophysics Data System (ADS)

    Heaps, Charles W.; Mazziotti, David A.

    2016-04-01

    Trajectory-based Gaussian basis sets have been tremendously successful in describing high-dimensional quantum molecular dynamics. In this paper, we introduce a pseudospectral Gaussian-based method that achieves accurate quantum dynamics using efficient, real-space sampling of the time-dependent basis set. As in other Gaussian basis methods, we begin with a basis set expansion using time-dependent Gaussian basis functions guided by classical mechanics. Unlike other Gaussian methods but characteristic of the pseudospectral and collocation methods, the basis set is tested with N Dirac delta functions, where N is the number of basis functions, rather than using the basis function as test functions. As a result, the integration for matrix elements is reduced to function evaluation. Pseudospectral Gaussian dynamics only requires O ( N ) potential energy calculations, in contrast to O ( N 2 ) evaluations in a variational calculation. The classical trajectories allow small basis sets to sample high-dimensional potentials. Applications are made to diatomic oscillations in a Morse potential and a generalized version of the Henon-Heiles potential in two, four, and six dimensions. Comparisons are drawn to full analytical evaluation of potential energy integrals (variational) and the bra-ket averaged Taylor (BAT) expansion, an O ( N ) approximation used in Gaussian-based dynamics. In all cases, the pseudospectral Gaussian method is competitive with full variational calculations that require a global, analytical, and integrable potential energy surface. Additionally, the BAT breaks down when quantum mechanical coherence is particularly strong (i.e., barrier reflection in the Morse oscillator). The ability to obtain variational accuracy using only the potential energy at discrete points makes the pseudospectral Gaussian method a promising avenue for on-the-fly dynamics, where electronic structure calculations become computationally significant.

  18. Pseudospectral Gaussian quantum dynamics: Efficient sampling of potential energy surfaces.

    PubMed

    Heaps, Charles W; Mazziotti, David A

    2016-04-28

    Trajectory-based Gaussian basis sets have been tremendously successful in describing high-dimensional quantum molecular dynamics. In this paper, we introduce a pseudospectral Gaussian-based method that achieves accurate quantum dynamics using efficient, real-space sampling of the time-dependent basis set. As in other Gaussian basis methods, we begin with a basis set expansion using time-dependent Gaussian basis functions guided by classical mechanics. Unlike other Gaussian methods but characteristic of the pseudospectral and collocation methods, the basis set is tested with N Dirac delta functions, where N is the number of basis functions, rather than using the basis function as test functions. As a result, the integration for matrix elements is reduced to function evaluation. Pseudospectral Gaussian dynamics only requires O(N) potential energy calculations, in contrast to O(N(2)) evaluations in a variational calculation. The classical trajectories allow small basis sets to sample high-dimensional potentials. Applications are made to diatomic oscillations in a Morse potential and a generalized version of the Henon-Heiles potential in two, four, and six dimensions. Comparisons are drawn to full analytical evaluation of potential energy integrals (variational) and the bra-ket averaged Taylor (BAT) expansion, an O(N) approximation used in Gaussian-based dynamics. In all cases, the pseudospectral Gaussian method is competitive with full variational calculations that require a global, analytical, and integrable potential energy surface. Additionally, the BAT breaks down when quantum mechanical coherence is particularly strong (i.e., barrier reflection in the Morse oscillator). The ability to obtain variational accuracy using only the potential energy at discrete points makes the pseudospectral Gaussian method a promising avenue for on-the-fly dynamics, where electronic structure calculations become computationally significant.

  19. Pseudospectral Gaussian quantum dynamics: Efficient sampling of potential energy surfaces.

    PubMed

    Heaps, Charles W; Mazziotti, David A

    2016-04-28

    Trajectory-based Gaussian basis sets have been tremendously successful in describing high-dimensional quantum molecular dynamics. In this paper, we introduce a pseudospectral Gaussian-based method that achieves accurate quantum dynamics using efficient, real-space sampling of the time-dependent basis set. As in other Gaussian basis methods, we begin with a basis set expansion using time-dependent Gaussian basis functions guided by classical mechanics. Unlike other Gaussian methods but characteristic of the pseudospectral and collocation methods, the basis set is tested with N Dirac delta functions, where N is the number of basis functions, rather than using the basis function as test functions. As a result, the integration for matrix elements is reduced to function evaluation. Pseudospectral Gaussian dynamics only requires O(N) potential energy calculations, in contrast to O(N(2)) evaluations in a variational calculation. The classical trajectories allow small basis sets to sample high-dimensional potentials. Applications are made to diatomic oscillations in a Morse potential and a generalized version of the Henon-Heiles potential in two, four, and six dimensions. Comparisons are drawn to full analytical evaluation of potential energy integrals (variational) and the bra-ket averaged Taylor (BAT) expansion, an O(N) approximation used in Gaussian-based dynamics. In all cases, the pseudospectral Gaussian method is competitive with full variational calculations that require a global, analytical, and integrable potential energy surface. Additionally, the BAT breaks down when quantum mechanical coherence is particularly strong (i.e., barrier reflection in the Morse oscillator). The ability to obtain variational accuracy using only the potential energy at discrete points makes the pseudospectral Gaussian method a promising avenue for on-the-fly dynamics, where electronic structure calculations become computationally significant. PMID:27131532

  20. Calculation of quasiparticle energy spectrum of silicon using the correlated Hartree-Fock method

    NASA Astrophysics Data System (ADS)

    Ishihara, Takamitsu; Yamagami, Hiroshi; Matsuzawa, Kazuya; Yasuhara, Hiroshi

    1999-06-01

    We present quasiparticle energy spectrum calculations of silicon using the correlated Hartree-Fock method proposed by Yasuhara and Takada [Phys. Rev. B 43, 7200 (1991)], in which the information on the effective mass of an electron liquid is included in the form of a nonlocal spin-parallel potential in addition to a local potential. The calculated band gaps of silicon are much improved, compared with the local density approximation values. The minimum indirect band gap is evaluated to be 1.37 eV.

  1. Three-dimensional potential energy surface of Ar–CO

    SciTech Connect

    Sumiyoshi, Yoshihiro; Endo, Yasuki

    2015-01-14

    A three-dimensional intermolecular potential energy surface of the Ar–CO complex has been determined by fitting most of the previously reported spectroscopic data, where observed transition frequencies by microwave, millimeter-wave, submillimeter-wave, and infrared spectroscopy were reproduced simultaneously within their experimental accuracies. A free rotor model Hamiltonian considering all the freedom of motions for an atom-diatom system was applied to calculate vibration-rotation energies. A three-dimensional potential energy surface obtained by ab initio calculations at the CCSD(T)-F12b/aug-cc-pV5Z level of theory was parameterized by a model function consisting of 46 parameters. They were used as initial values for the least-squares analysis of the experimental data. A total of 20 parameters were optimized to reproduce all the spectroscopic data.

  2. N2(+) bound quartet and sextet state potential energy curves

    NASA Technical Reports Server (NTRS)

    Partridge, H.; Bauschlicher, C. W., Jr.; Stallcop, J. R.

    1985-01-01

    The N2(+) potential energies have been determined from a complete active space self-consistent field calculation with active 2s and 2p electrons. A (6s 4p 3d 1f) Gaussian basis set was used together with additional higher angular momentum and diffuse functions. The calculated potential energy curves for the states 4Sigma(mu)(+), 4Pi(g), and 6Sigma(g)(+), for which there are no spectroscopic observations, are presented. The corresponding spectroscopic constants have been determined from a polynomial curve fit to the computed energies near the well minima and are shown. The 6Sigma(g)(+) state is found to be significantly bound, with a minimum at 1.72 A.

  3. Variational Approach to Enhanced Sampling and Free Energy Calculations

    NASA Astrophysics Data System (ADS)

    Valsson, Omar; Parrinello, Michele

    2014-08-01

    The ability of widely used sampling methods, such as molecular dynamics or Monte Carlo simulations, to explore complex free energy landscapes is severely hampered by the presence of kinetic bottlenecks. A large number of solutions have been proposed to alleviate this problem. Many are based on the introduction of a bias potential which is a function of a small number of collective variables. However constructing such a bias is not simple. Here we introduce a functional of the bias potential and an associated variational principle. The bias that minimizes the functional relates in a simple way to the free energy surface. This variational principle can be turned into a practical, efficient, and flexible sampling method. A number of numerical examples are presented which include the determination of a three-dimensional free energy surface. We argue that, beside being numerically advantageous, our variational approach provides a convenient and novel standpoint for looking at the sampling problem.

  4. Wind energy in China: Estimating the potential

    NASA Astrophysics Data System (ADS)

    Yuan, Jiahai

    2016-07-01

    Persistent and significant curtailment has cast concern over the prospects of wind power in China. A comprehensive assessment of the production of energy from wind has identified grid-integrated wind generation potential at 11.9–14% of China's projected energy demand by 2030.

  5. Nonequilibrium molecular transport photoinduced by potential energy fluctuations

    NASA Astrophysics Data System (ADS)

    Dekhtyar, Marina L.; Rozenbaum, Viktor M.

    2011-01-01

    The mechanism of directed substrate-parallel motion of molecules caused by photoinduced potential energy fluctuations is investigated. Unlike simplistic models (e.g., an on-off ratchet), the approach suggested implies that the necessary asymmetry of the potential energy can arise not only from the asymmetry of the substrate potential but also from an asymmetric distribution of the fluctuating charge density in the molecule. The thus induced asymmetry of the potential energy governs the direction motion and enables, under certain conditions, its reversal at some frequencies of resonant laser pulses or temperature. These inferences are exemplified by the model charge distributions in the molecule and substrate, and the charge density fluctuations which are obtained by quantum chemical calculations for the realistic molecule of a substituted phenylpyrene compound on a model substrate.

  6. Economic Energy Savings Potential in Federal Buildings

    SciTech Connect

    Brown, Daryl R.; Dirks, James A.; Hunt, Diane M.

    2000-09-04

    The primary objective of this study was to estimate the current life-cycle cost-effective (i.e., economic) energy savings potential in Federal buildings and the corresponding capital investment required to achieve these savings, with Federal financing. Estimates were developed for major categories of energy efficiency measures such as building envelope, heating system, cooling system, and lighting. The analysis was based on conditions (building stock and characteristics, retrofit technologies, interest rates, energy prices, etc.) existing in the late 1990s. The potential impact of changes to any of these factors in the future was not considered.

  7. SCALE Continuous-Energy Eigenvalue Sensitivity Coefficient Calculations

    DOE PAGES

    Perfetti, Christopher M.; Rearden, Bradley T.; Martin, William R.

    2016-02-25

    Sensitivity coefficients describe the fractional change in a system response that is induced by changes to system parameters and nuclear data. The Tools for Sensitivity and UNcertainty Analysis Methodology Implementation (TSUNAMI) code within the SCALE code system makes use of eigenvalue sensitivity coefficients for an extensive number of criticality safety applications, including quantifying the data-induced uncertainty in the eigenvalue of critical systems, assessing the neutronic similarity between different critical systems, and guiding nuclear data adjustment studies. The need to model geometrically complex systems with improved fidelity and the desire to extend TSUNAMI analysis to advanced applications has motivated the developmentmore » of a methodology for calculating sensitivity coefficients in continuous-energy (CE) Monte Carlo applications. The Contributon-Linked eigenvalue sensitivity/Uncertainty estimation via Tracklength importance CHaracterization (CLUTCH) and Iterated Fission Probability (IFP) eigenvalue sensitivity methods were recently implemented in the CE-KENO framework of the SCALE code system to enable TSUNAMI-3D to perform eigenvalue sensitivity calculations using continuous-energy Monte Carlo methods. This work provides a detailed description of the theory behind the CLUTCH method and describes in detail its implementation. This work explores the improvements in eigenvalue sensitivity coefficient accuracy that can be gained through the use of continuous-energy sensitivity methods and also compares several sensitivity methods in terms of computational efficiency and memory requirements.« less

  8. Exploiting the Properties of Aquaporin to Calculate Free Energy

    NASA Astrophysics Data System (ADS)

    Espejel, Hugo; Chen, Liao

    2010-03-01

    Aquaporins' (AQPs) main purpose is to facilitate the transfer of water molecules through a molecular membrane. We can calculate the free energy of the AQP system when water permeates through it. This is performed using the Visual Molecular Dynamics (VMD) and the Nanoscale Molecular Dynamics (NAMD) programs. In our first set of experiments, AQP is submerged in a body of water, in which case a water molecule near AQP is pulled through the protein. The data is then used to calculate the free energy using two different equations: the Jarzynski equality and the fluctuation-dissipation theorem. The values from both equations are then compared to examine their accuracy. The second set of experiments has the same set up, but now AQP is embedded in a lipid bilayer. We found that both equations give values that are much smaller than kT. This verifies that AQP is a channel for water molecules because the pulling of water gives constant values of free energy. We also found that the water molecules' negative poles were all pointing towards the center of the AQP channel. This means that the process of proton transport in AQP is overwhelmingly difficult.

  9. High-energy photoelectron diffraction: model calculations and future possibilities

    NASA Astrophysics Data System (ADS)

    Winkelmann, Aimo; Fadley, Charles S.; Garcia de Abajo, F. Javier

    2008-11-01

    We discuss the theoretical modeling of x-ray photoelectron diffraction (XPD) with hard x-ray excitation at up to 20 keV, using the dynamical theory of electron diffraction to illustrate the characteristic aspects of the diffraction patterns resulting from such localized emission sources in a multilayer crystal. We show via dynamical calculations for diamond, Si and Fe that the dynamical theory predicts well the available current data for lower energies around 1 keV, and that the patterns for energies above about 1 keV are dominated by Kikuchi bands, which are created by the dynamical scattering of electrons from lattice planes. The origin of the fine structure in such bands is discussed from the point of view of atomic positions in the unit cell. The profiles and positions of the element-specific photoelectron Kikuchi bands are found to be sensitive to lattice distortions (e.g. a 1% tetragonal distortion) and the position of impurities or dopants with respect to lattice sites. We also compare the dynamical calculations with results from a cluster model that is more often used to describe lower energy XPD. We conclude that hard XPD (HXPD) should be capable of providing unique bulk-sensitive structural information for a wide variety of complex materials in future experiments.

  10. Applying supersymmetry to energy dependent potentials

    SciTech Connect

    Yekken, R.; Lassaut, M.; Lombard, R.J.

    2013-11-15

    We investigate the supersymmetry properties of energy dependent potentials in the D=1 dimensional space. We show the main aspects of supersymmetry to be preserved, namely the factorization of the Hamiltonian, the connections between eigenvalues and wave functions of the partner Hamiltonians. Two methods are proposed. The first one requires the extension of the usual rules via the concept of local equivalent potential. In this case, the superpotential becomes depending on the state. The second method, applicable when the potential depends linearly on the energy, is similar to what has been already achieved by means of the Darboux transform. -- Highlights: •Supersymmetry extended to energy dependent potentials. •Generalization of the concept of superpotential. •An alternative method used for linear E-dependence leads to the same results as Darboux transform.

  11. Free Energies of Redox Half-Reactions from First-Principles Calculations.

    PubMed

    Tazhigulov, Ruslan N; Bravaya, Ksenia B

    2016-07-01

    Quantitative prediction of the energetics of redox half-reactions is still a challenge for modern computational chemistry. Here, we propose a simple scheme for reliable calculations of vertical ionization and attachment energies, as well as of redox potentials of solvated molecules. The approach exploits linear response approximation in the context of explicit solvent simulations with spherical boundary conditions. It is shown that both vertical ionization energies and vertical electron affinities, and, consequently redox potentials, exhibit linear dependence on the inverse radius of the solvation sphere. The explanation of the linear dependence is provided, and an extrapolation scheme is suggested. The proposed approach accounts for the specific short-range interactions within hybrid DFT and effective fragment potential approach as well as for the asymptotic system-size effects. The computed vertical ionization energies and redox potentials are in excellent agreement with the experimental values.

  12. AlaScan: A Graphical User Interface for Alanine Scanning Free-Energy Calculations.

    PubMed

    Ramadoss, Vijayaraj; Dehez, François; Chipot, Christophe

    2016-06-27

    Computation of the free-energy changes that underlie molecular recognition and association has gained significant importance due to its considerable potential in drug discovery. The massive increase of computational power in recent years substantiates the application of more accurate theoretical methods for the calculation of binding free energies. The impact of such advances is the application of parent approaches, like computational alanine scanning, to investigate in silico the effect of amino-acid replacement in protein-ligand and protein-protein complexes, or probe the thermostability of individual proteins. Because human effort represents a significant cost that precludes the routine use of this form of free-energy calculations, minimizing manual intervention constitutes a stringent prerequisite for any such systematic computation. With this objective in mind, we propose a new plug-in, referred to as AlaScan, developed within the popular visualization program VMD to automate the major steps in alanine-scanning calculations, employing free-energy perturbation as implemented in the widely used molecular dynamics code NAMD. The AlaScan plug-in can be utilized upstream, to prepare input files for selected alanine mutations. It can also be utilized downstream to perform the analysis of different alanine-scanning calculations and to report the free-energy estimates in a user-friendly graphical user interface, allowing favorable mutations to be identified at a glance. The plug-in also assists the end-user in assessing the reliability of the calculation through rapid visual inspection.

  13. Large magnetocrystalline anisotropy in bilayer transition metal phases from first-principles full-potential calculations

    NASA Astrophysics Data System (ADS)

    Ravindran, P.; Kjekshus, A.; Fjellvåg, H.; James, P.; Nordström, L.; Johansson, B.; Eriksson, O.

    2001-04-01

    The computational framework of this study is based on the local-spin-density approximation with first-principles full-potential linear muffin-tin orbital calculations including orbital polarization (OP) correction. We have studied the magnetic anisotropy for a series of bilayer CuAu(I)-type materials such as FeX, MnX (X=Ni,Pd,Pt), CoPt, NiPt, MnHg, and MnRh in a ferromagnetic state using experimental structural parameters to understand the microscopic origin of magnetic-anisotropy energy (MAE) in magnetic multilayers. Except for MnRh and MnHg, all these phases show perpendicular magnetization. We have analyzed our results in terms of angular momentum-, spin- and site-projected density of states, magnetic-angular-momentum-projected density of states, orbital-moment density of states, and total density of states. The orbital-moment number of states and the orbital-moment anisotropy for FeX (X=Ni,Pd,Pt) are calculated as a function of band filling to study its effect on MAE. The total and site-projected spin and orbital moments for all these systems are calculated with and without OP when the magnetization is along or perpendicular to the plane. The results are compared with available experimental as well as theoretical results. Our calculations show that OP always enhances the orbital moment in these phases and brings them closer to experimental values. The changes in MAE are analyzed in terms of exchange splitting, spin-orbit splitting, and tetragonal distortion/crystal-field splitting. The calculated MAE is found to be in good agreement with experimental values when the OP correction is included. Some of the materials considered here show large magnetic anisotropy of the order of meV. In particular we found that MnPt will have a very large MAE if it could be stabilized in a ferromagnetic configuration. Our analysis indicates that apart from large spin-orbit interaction and exchange interaction from at least one of the constituents, a large crystal-field splitting

  14. Parquet decomposition calculations of the electronic self-energy

    NASA Astrophysics Data System (ADS)

    Gunnarsson, O.; Schäfer, T.; LeBlanc, J. P. F.; Merino, J.; Sangiovanni, G.; Rohringer, G.; Toschi, A.

    2016-06-01

    The parquet decomposition of the self-energy into classes of diagrams, those associated with specific scattering processes, can be exploited for different scopes. In this work, the parquet decomposition is used to unravel the underlying physics of nonperturbative numerical calculations. We show the specific example of dynamical mean field theory and its cluster extensions [dynamical cluster approximation (DCA)] applied to the Hubbard model at half-filling and with hole doping: These techniques allow for a simultaneous determination of two-particle vertex functions and self-energies and, hence, for an essentially "exact" parquet decomposition at the single-site or at the cluster level. Our calculations show that the self-energies in the underdoped regime are dominated by spin-scattering processes, consistent with the conclusions obtained by means of the fluctuation diagnostics approach [O. Gunnarsson et al., Phys. Rev. Lett. 114, 236402 (2015), 10.1103/PhysRevLett.114.236402]. However, differently from the latter approach, the parquet procedure displays important changes with increasing interaction: Even for relatively moderate couplings, well before the Mott transition, singularities appear in different terms, with the notable exception of the predominant spin channel. We explain precisely how these singularities, which partly limit the utility of the parquet decomposition and, more generally, of parquet-based algorithms, are never found in the fluctuation diagnostics procedure. Finally, by a more refined analysis, we link the occurrence of the parquet singularities in our calculations to a progressive suppression of charge fluctuations and the formation of a resonance valence bond state, which are typical hallmarks of a pseudogap state in DCA.

  15. Energy savings potential in air conditioners and chiller systems

    DOE PAGES

    Kaya, Durmus; Alidrisi, Hisham

    2014-01-22

    In the current paper we quantified and evaluated the energy saving potential in air conditioners and chiller systems. Here, we also showed how to reduce the cost of air conditioners and chiller systems in existing facilities on the basis of payback periods. Among the measures investigated were: (1) installing higher efficiency air conditioners, (2) installing higher efficiency chillers, (3) duty cycling air conditioning units, and (4) utilizing existing economizers on air conditioning units. For each method, examples were provided from Arizona, USA. In these examples, the amount of saved energy, the financial evaluation of this energy, and the investment costmore » and pay back periods were calculated.« less

  16. Energy savings potential in air conditioners and chiller systems

    SciTech Connect

    Kaya, Durmus; Alidrisi, Hisham

    2014-01-22

    In the current paper we quantified and evaluated the energy saving potential in air conditioners and chiller systems. Here, we also showed how to reduce the cost of air conditioners and chiller systems in existing facilities on the basis of payback periods. Among the measures investigated were: (1) installing higher efficiency air conditioners, (2) installing higher efficiency chillers, (3) duty cycling air conditioning units, and (4) utilizing existing economizers on air conditioning units. For each method, examples were provided from Arizona, USA. In these examples, the amount of saved energy, the financial evaluation of this energy, and the investment cost and pay back periods were calculated.

  17. An algorithm for the uniform sampling of iso-energy surfaces and for the calculation of microcanonical averages.

    PubMed

    Rapallo, Arnaldo

    2006-03-01

    In this article an algorithm is proposed to efficiently perform the uniform sampling of an iso-energy surface corresponding to a fixed potential energy U of a molecular system, and for calculating averages of certain quantities over microstates having this energy (microcanonical averages). The developed sampling technique is based upon the combination of a recently proposed method for performing constant potential energy molecular dynamics simulations [Rapallo, A. J Chem Phys 2004, 121, 4033] with well-established thermostatting techniques used in the framework of standard molecular dynamics simulations, such as the Andersen thermostat, and the Nose-Hoover chain thermostat. The proposed strategy leads to very accurate and drift-free potential energy conservation during the whole sampling process, and, very important, specially when dealing with high-dimensional or complicated potential functions, it does not require the calculation of the potential energy function hessian. The technique proved to be very reliable for sampling both low- and high-dimensional surfaces.

  18. Empirically corrected HEAT method for calculating atomization energies

    SciTech Connect

    Brand, Holmann V

    2008-01-01

    We describe how to increase the accuracy ofthe most recent variants ofthe HEAT method for calculating atomization energies of molecules by means ofextremely simple empirical corrections that depend on stoichiometry and the number ofunpaired electrons in the molecule. Our corrections reduce the deviation from experiment for all the HEAT variants. In particular, our corrections reduce the average absolute deviation and the root-mean-square deviation ofthe 456-QP variant to 0.18 and 0.23 kJoule/mol (i.e., 0.04 and 0.05 kcallmol), respectively.

  19. Energy conservation in Kenya: progress, potentials, problems

    SciTech Connect

    Schipper, L.; Hollander, J.M.; Milukas, M.; Alcamo, J.; Meyers, S.; Noll, S.

    1981-09-01

    A study was carried out of the flows of commercial energy in the economy of Kenya. Indications were sought of the extent to which energy conservation, (i.e., increase in efficiency of energy use) has reduced the ratio of energy inputs to economic outputs, in the post-1973 years. An assessment was made of the potential for energy conservation to reduce the growth of Kenyan energy use in the future and of significant barriers to increasing energy efficiency. Consideration was given to the role of government policy and of international assistance in fostering energy conservation in Kenya and other developing countries. The study was performed by analyzing available energy data and statistics from the largest oil companies, the Kenyan electric utility, and the government. These sources were supplemented by conducting personal interviews with personnel of nearly 50 commercial firms in Kenya. Direct consumption of fuel accounts for 94% of the commercial energy use in Kenya, while electricity accounts for 6%. The sectoral division of fuel use is: transportation 53%, industry 21%, energy production 11%, agriculture 9%, buildings and residences 5%, and construction 1%. For electricity the division is: buildings and residences 48%, industry 45%, energy production 4%, agriculture 2%, and construction 1%. Recent progress in conservation is reported.

  20. Potential energy surface and rovibrational energy levels of the H2-CS van der Waals complex.

    PubMed

    Denis-Alpizar, Otoniel; Stoecklin, Thierry; Halvick, Philippe; Dubernet, Marie-Lise; Marinakis, Sarantos

    2012-12-21

    Owing to its large dipole, astrophysicists use carbon monosulfide (CS) as a tracer of molecular gas in the interstellar medium, often in regions where H(2) is the most abundant collider. Predictions of the rovibrational energy levels of the weakly bound complex CS-H(2) (not yet observed) and also of rate coefficients for rotational transitions of CS in collision with H(2) should help to interpret the observed spectra. This paper deals with the first goal, i.e., the calculation of the rovibrational energy levels. A new four-dimensional intermolecular potential energy surface for the H(2)-CS complex is presented. Ab initio potential energy calculations were carried out at the coupled-cluster level with single and double excitations and a perturbative treatment of triple excitations, using a quadruple-zeta basis set and midbond functions. The potential energy surface was obtained by an analytic fit of the ab initio data. The equilibrium structure of the H(2)-CS complex is found to be linear with the carbon pointing toward H(2) at the intermolecular separation of 8.6 a(o). The corresponding well depth is -173 cm(-1). The potential was used to calculate the rovibrational energy levels of the para-H(2)-CS and ortho-H(2)-CS complexes. The present work provides the first theoretical predictions of these levels. The calculated dissociation energies are found to be 35.9 cm(-1) and 49.9 cm(-1), respectively, for the para and ortho complexes. The second virial coefficient for the H(2)-CS pair has also been calculated for a large range of temperature. These results could be used to assign future experimental spectra and to check the accuracy of the potential energy surface.

  1. Calculation of the bidimensional electric potential in a polycrystalline semiconductor Schottky junction

    NASA Astrophysics Data System (ADS)

    Mudrik, M.; Croitoru, N.

    1986-09-01

    In a Schottky p-type polycrystalline junction, two kinds of space-charge layers exist, one due to junction and the other due to the grain boundaries (GB). In such a case, the potential V( x, y) is a solution of a two-dimensional Poisson equation, where x is the distance from the junction and y from the GB. A case is considered where the crystallites are columnar, all the grains are identical, and the doping concentration is N Acm-3. We assume that the GB introduces energy states (i.e. traps) which are equivalent with another effective doping NBcm-3. The existence of a junction perpendicular to the GB causes the width of the GB space charge to decrease. The interaction between the two space charges is expressed by a parameter γ = ( WB0 - WB(0)/ WJ, where W B0 and WB(0) are the widths of the GB space charge without, and with, a Schottky junction, respectively, and W J is the width of the space charge of the junction. The Poisson equation is solved and the potential is V(x,y)= {qN A}/{2ɛ}x 2+ {N B}/{N A}y 2-γ {N B}/{N A}xy- 2W j-γ {N B}/{N A}W 0Bx- {N B}/{N A}[W B(0)+W 0B]y . The term- γqNB xy/2 ɛ appears due to the interaction of both space charges. The electric field, the GB energy barrier and the capacitance are calculated from the potential and are x and y dependent. An equivalent circuit for the distribution of space charges is obtained and could be used in the interpretation of experimental results.

  2. Numerical Green's functions in optical potential calculations for positron scattering from argon and neon

    NASA Technical Reports Server (NTRS)

    Bartschat, K.; Mceachran, R. P.; Stauffer, A. D.

    1990-01-01

    An optical potential method was applied to the calculation of positron scattering from the noble gases in order to determine the effect of open excitation channels on the shape of differential scattering cross sections.

  3. Using the charge-stabilization technique in the double ionization potential equation-of-motion calculations with dianion references.

    PubMed

    Kuś, Tomasz; Krylov, Anna I

    2011-08-28

    The charge-stabilization method is applied to double ionization potential equation-of-motion (EOM-DIP) calculations to stabilize unstable dianion reference functions. The auto-ionizing character of the dianionic reference states spoils the numeric performance of EOM-DIP limiting applications of this method. We demonstrate that reliable excitation energies can be computed by EOM-DIP using a stabilized resonance wave function instead of the lowest energy solution corresponding to the neutral + free electron(s) state of the system. The details of charge-stabilization procedure are discussed and illustrated by examples. The choice of optimal stabilizing Coulomb potential, which is strong enough to stabilize the dianion reference, yet, minimally perturbs the target states of the neutral, is the crux of the approach. Two algorithms of choosing optimal parameters of the stabilization potential are presented. One is based on the orbital energies, and another--on the basis set dependence of the total Hartree-Fock energy of the reference. Our benchmark calculations of the singlet-triplet energy gaps in several diradicals show a remarkable improvement of the EOM-DIP accuracy in problematic cases. Overall, the excitation energies in diradicals computed using the stabilized EOM-DIP are within 0.2 eV from the reference EOM spin-flip values.

  4. 40 CFR Appendix D to Part 72 - Calculation of Potential Electric Output Capacity

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 17 2013-07-01 2013-07-01 false Calculation of Potential Electric Output Capacity D Appendix D to Part 72 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) PERMITS REGULATION Pt. 72, App. D Appendix D to Part 72—Calculation...

  5. 40 CFR Appendix D to Part 72 - Calculation of Potential Electric Output Capacity

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 16 2010-07-01 2010-07-01 false Calculation of Potential Electric Output Capacity D Appendix D to Part 72 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) PERMITS REGULATION Pt. 72, App. D Appendix D to Part 72—Calculation...

  6. Nuclear binding energy and symmetry energy of nuclear matter with modern nucleon-nucleon potentials

    SciTech Connect

    Hassaneen, Kh.S.A.; Abo-Elsebaa, H.M.; Sultan, E.A.; Mansour, H.M.M.

    2011-03-15

    Research Highlights: > The nuclear matter is studied within the Brueckner-Hartree-Fock (BHF) approach employing the most recent accurate nucleon-nucleon potentials. > The results come out by approximating the single particle self-consistent potential with a parabolic form. > We discuss the current status of the Coester line, i.e., density and energy of the various saturation points being strongly linearly correlated. > The nuclear symmetry energy is calculated as the difference between the binding energy of pure neutron matter and that of symmetric nuclear matter. - Abstract: The binding energy of nuclear matter at zero temperature in the Brueckner-Hartree-Fock approximation with modern nucleon-nucleon potentials is studied. Both the standard and continuous choices of single particle energies are used. These modern nucleon-nucleon potentials fit the deuteron properties and are phase shifts equivalent. Comparison with other calculations is made. In addition we present results for the symmetry energy obtained with different potentials, which is of great importance in astrophysical calculation.

  7. Crystal-field calculations for transition-metal ions by application of an opposing potential

    DOE PAGES

    Zhou, Fei; Aberg, Daniel

    2016-02-16

    We propose a fully ab initio method, the opposing crystal potential (OCP), to calculate the crystal-field parameters of transition-metal impurities in insulator hosts. Through constrained density functional calculations, OCP obtains the constraining Lagrange multipliers, which act as a cancellation potential against the crystal field and lead to spherical d-electron distribution. Furthermore, the method is applied to several insulators doped with Mn4+ and Mn2+ ions and shown to be in good agreement with experiment.

  8. Communication: Fitting potential energy surfaces with fundamental invariant neural network

    NASA Astrophysics Data System (ADS)

    Shao, Kejie; Chen, Jun; Zhao, Zhiqiang; Zhang, Dong H.

    2016-08-01

    A more flexible neural network (NN) method using the fundamental invariants (FIs) as the input vector is proposed in the construction of potential energy surfaces for molecular systems involving identical atoms. Mathematically, FIs finitely generate the permutation invariant polynomial (PIP) ring. In combination with NN, fundamental invariant neural network (FI-NN) can approximate any function to arbitrary accuracy. Because FI-NN minimizes the size of input permutation invariant polynomials, it can efficiently reduce the evaluation time of potential energy, in particular for polyatomic systems. In this work, we provide the FIs for all possible molecular systems up to five atoms. Potential energy surfaces for OH3 and CH4 were constructed with FI-NN, with the accuracy confirmed by full-dimensional quantum dynamic scattering and bound state calculations.

  9. Communication: Fitting potential energy surfaces with fundamental invariant neural network.

    PubMed

    Shao, Kejie; Chen, Jun; Zhao, Zhiqiang; Zhang, Dong H

    2016-08-21

    A more flexible neural network (NN) method using the fundamental invariants (FIs) as the input vector is proposed in the construction of potential energy surfaces for molecular systems involving identical atoms. Mathematically, FIs finitely generate the permutation invariant polynomial (PIP) ring. In combination with NN, fundamental invariant neural network (FI-NN) can approximate any function to arbitrary accuracy. Because FI-NN minimizes the size of input permutation invariant polynomials, it can efficiently reduce the evaluation time of potential energy, in particular for polyatomic systems. In this work, we provide the FIs for all possible molecular systems up to five atoms. Potential energy surfaces for OH3 and CH4 were constructed with FI-NN, with the accuracy confirmed by full-dimensional quantum dynamic scattering and bound state calculations.

  10. Communication: Fitting potential energy surfaces with fundamental invariant neural network.

    PubMed

    Shao, Kejie; Chen, Jun; Zhao, Zhiqiang; Zhang, Dong H

    2016-08-21

    A more flexible neural network (NN) method using the fundamental invariants (FIs) as the input vector is proposed in the construction of potential energy surfaces for molecular systems involving identical atoms. Mathematically, FIs finitely generate the permutation invariant polynomial (PIP) ring. In combination with NN, fundamental invariant neural network (FI-NN) can approximate any function to arbitrary accuracy. Because FI-NN minimizes the size of input permutation invariant polynomials, it can efficiently reduce the evaluation time of potential energy, in particular for polyatomic systems. In this work, we provide the FIs for all possible molecular systems up to five atoms. Potential energy surfaces for OH3 and CH4 were constructed with FI-NN, with the accuracy confirmed by full-dimensional quantum dynamic scattering and bound state calculations. PMID:27544080

  11. A Variational Approach to Enhanced Sampling and Free Energy Calculations

    NASA Astrophysics Data System (ADS)

    Parrinello, Michele

    2015-03-01

    The presence of kinetic bottlenecks severely hampers the ability of widely used sampling methods like molecular dynamics or Monte Carlo to explore complex free energy landscapes. One of the most popular methods for addressing this problem is umbrella sampling which is based on the addition of an external bias which helps overcoming the kinetic barriers. The bias potential is usually taken to be a function of a restricted number of collective variables. However constructing the bias is not simple, especially when the number of collective variables increases. Here we introduce a functional of the bias which, when minimized, allows us to recover the free energy. We demonstrate the usefulness and the flexibility of this approach on a number of examples which include the determination of a six dimensional free energy surface. Besides the practical advantages, the existence of such a variational principle allows us to look at the enhanced sampling problem from a rather convenient vantage point.

  12. A study of potential numerical pitfalls in GPU-based Monte Carlo dose calculation

    NASA Astrophysics Data System (ADS)

    Magnoux, Vincent; Ozell, Benoît; Bonenfant, Éric; Després, Philippe

    2015-07-01

    The purpose of this study was to evaluate the impact of numerical errors caused by the floating point representation of real numbers in a GPU-based Monte Carlo code used for dose calculation in radiation oncology, and to identify situations where this type of error arises. The program used as a benchmark was bGPUMCD. Three tests were performed on the code, which was divided into three functional components: energy accumulation, particle tracking and physical interactions. First, the impact of single-precision calculations was assessed for each functional component. Second, a GPU-specific compilation option that reduces execution time as well as precision was examined. Third, a specific function used for tracking and potentially more sensitive to precision errors was tested by comparing it to a very high-precision implementation. Numerical errors were found in two components of the program. Because of the energy accumulation process, a few voxels surrounding a radiation source end up with a lower computed dose than they should. The tracking system contained a series of operations that abnormally amplify rounding errors in some situations. This resulted in some rare instances (less than 0.1%) of computed distances that are exceedingly far from what they should have been. Most errors detected had no significant effects on the result of a simulation due to its random nature, either because they cancel each other out or because they only affect a small fraction of particles. The results of this work can be extended to other types of GPU-based programs and be used as guidelines to avoid numerical errors on the GPU computing platform.

  13. Separable representation of energy-dependent optical potentials

    NASA Astrophysics Data System (ADS)

    Hlophe, L.; Elster, Ch.

    2016-03-01

    Background: One important ingredient for many applications of nuclear physics to astrophysics, nuclear energy, and stockpile stewardship are cross sections for reactions of neutrons with rare isotopes. Since direct measurements are often not feasible, indirect methods, e.g., (d ,p ) reactions, should be used. Those (d ,p ) reactions may be viewed as three-body reactions and described with Faddeev techniques. Purpose: Faddeev equations in momentum space have a long tradition of utilizing separable interactions in order to arrive at sets of coupled integral equations in one variable. Optical potentials representing the effective interactions in the neutron (proton) nucleus subsystem are usually non-Hermitian as well as energy dependent. Potential matrix elements as well as transition matrix elements calculated with them must fulfill the reciprocity theorem. The purpose of this paper is to introduce a separable, energy-dependent representation of complex, energy-dependent optical potentials that fulfill reciprocity exactly. Methods: Momentum space Lippmann-Schwinger integral equations are solved with standard techniques to obtain the form factors for the separable representation. Results: Starting from a separable, energy-independent representation of global optical potentials based on a generalization of the Ernst-Shakin-Thaler (EST) scheme, a further generalization is needed to take into account the energy dependence. Applications to n +48Ca ,n +208Pb , and p +208Pb are investigated for energies from 0 to 50 MeV with special emphasis on fulfilling reciprocity. Conclusions: We find that the energy-dependent separable representation of complex, energy-dependent phenomenological optical potentials fulfills reciprocity exactly. In addition, taking into account the explicit energy dependence slightly improves the description of the S matrix elements.

  14. Biomass resource potential using energy crops

    SciTech Connect

    Wright, L.L.; Cushman, J.H.; Martin, S.A.

    1993-09-01

    Biomass energy crops can provide a significant and environmentally beneficial source of renewable energy feedstocks for the future. They can revitalize the agricultural sector of the US economy by providing profitable uses for marginal cropland. Energy crops include fast-growing trees, perennial grasses, and annual grasses, all capable of collecting solar energy and storing it as cellulosic compounds for several months to several years. Once solar energy is thus captured, it can be converted by means of currently available technologies to a wide variety of energy products such as electricity, heat, liquid transportation fuels, and gases. Experimental results from field trials have generated optimism that selected and improved energy crops, established on cropland with moderate limitations for crop production, have the potential for producing high yields. Both trees and grasses, under very good growing conditions, have produced average annual yields of 20 to 40 dry Mg ha{sup {minus}1} year{sup {minus}1}. Sorghum has shown especially high yields in the Midwest. Hybrids between sugar cane and its wild relatives, called energy cane, have yielded as much as 50 dry Mg ha{sup {minus}1} year{sup {minus}1} in Florida. These experimental results demonstrate that some species have the genetic potential for very rapid growth rates. New wood energy crop systems developed by the Department of Energy`s Biofuels Feedstock Development Program offer, at a minimum, a 100% increase in biomass production rates over the 2 to 4 Mg ha{sup {minus}1} year{sup {minus}1} of dry leafless woody biomass produced by most natural forest systems. Experimental data indicate that short rotation wood crops established on cropland with moderate limitations are capable of producing biomass yields of 8--20 dry Mg ha{sup {minus}1} year{sup {minus}1} with a present average about 11 dry Mg ha{sup {minus}1} year{sup {minus}1} on typical cropland sites.

  15. Two-loop Feynman-gauge calculation of the meson nonsinglet evolution potential

    SciTech Connect

    Katz, G.R.

    1985-02-01

    Recently, three independent determinations of the two-loop meson nonsinglet evolution potential have been completed. Two of them are an explicit light-cone-gauge calculation while the third is a less direct evaluation based on conformal symmetry. However, all three calculations disagree in the C/sub F/ /sup 2/ term. In this paper I present the results of a Feynman-gauge evaluation of Gegenbauer matrix elements (V/sub 2/)/sub mj/ of the C/sub F/ /sup 2/ part of the two-loop meson nonsinglet evolution potential. The results confirm one of the light-cone-gauge calculations.

  16. Analysis of the quasi-static approximation for calculating potentials generated by neural stimulation

    NASA Astrophysics Data System (ADS)

    Bossetti, Chad A.; Birdno, Merrill J.; Grill, Warren M.

    2008-03-01

    In models of electrical stimulation of the nervous system, the electric potential is typically calculated using the quasi-static approximation. The quasi-static approximation allows Maxwell's equations to be simplified by ignoring capacitive, inductive and wave propagation contributions to the potential. While this simplification has been validated for bioelectric sources, its application to rapid stimulation pulses, which contain more high-frequency power, may not be appropriate. We compared the potentials calculated using the quasi-static approximation with those calculated from the exact solution to the inhomogeneous Helmholtz equation. The mean absolute errors between the two potential calculations were limited to 5-13% for pulse widths commonly used for neural stimulation (25 µs-1 ms). We also quantified the excitation properties of extracellular point source stimulation of a myelinated nerve fiber model using potentials calculated from each method. Deviations between the strength-duration curves for potentials calculated using the quasi-static (σ = 0.105 S m-1) and Helmholtz approaches ranged from 3 to 16%, with the minimal error occurring for 100 µs pulses. Differences in the threshold-distance curves for the two calculations ranged from 0 to 9%, for the same value of quasi-static conductivity. A sensitivity analysis of the material parameters revealed that the potential was much more strongly dependent on the conductivity than on the permittivity. These results indicate that for commonly used stimulus pulse parameters, the exact solution for the potential can be approximated by quasi-static simplifications only for appropriate values of conductivity.

  17. Measurements and calculations of neutron scattering angular distributions over a wide mass and energy range

    SciTech Connect

    Hansen, L.F.

    1985-05-01

    Neutron elastic and inelastic differential cross sections for targets between /sup 9/Be and /sup 239/Pu at energies, E > 14 MeV have been measured using the Livermore and Ohio University neutron time-of-flight facilities. We review here the data and the analyses based on two local microscopic optical potentials: that of Jeukenne, Lejeune and Mahaux, and that of Brieva and Rook. The results are also compared with calculations using global potentials. Coupled channel formalism has been used in the analysis of targets with strong deformations, such as Be, C, Ta, and actinides. The value of the microscopic optical potentials as a tool to predict elastic and inelastic neutron cross sections over a wide mass and energy range is discussed. The need for neutron measurements up to higher energies and their analysis in conjunction with (p,p) and charge exchange (p,n) data is addressed. 17 refs.

  18. Potential reduction of DSN uplink energy cost

    NASA Technical Reports Server (NTRS)

    Dolinsky, S.; Degroot, N. F.

    1982-01-01

    DSN Earth stations typically transmit more power than that required to meet minimum specifications for uplink performance. Energy and cost savings that could result from matching the uplink power to the amount required for specified performance are studied. The Galileo mission was selected as a case study. Although substantial reduction in transmitted energy is possible, potential savings in source energy (oil or electricity) savings are much less. This is because of the rising inefficiency in power conversion and radio frequency power generation that accompanies reduced power output.

  19. Parallel AFMPB solver with automatic surface meshing for calculation of molecular solvation free energy

    NASA Astrophysics Data System (ADS)

    Zhang, Bo; Peng, Bo; Huang, Jingfang; Pitsianis, Nikos P.; Sun, Xiaobai; Lu, Benzhuo

    2015-05-01

    We present PAFMPB, an updated and parallel version of the AFMPB software package for fast calculation of molecular solvation-free energy. The new version has the following new features: (1) The adaptive fast multipole method and the boundary element methods are parallelized; (2) A tool is embedded for automatic molecular VDW/SAS surface mesh generation, leaving the requirement for a mesh file at input optional; (3) The package provides fast calculation of the total solvation-free energy, including the PB electrostatic and nonpolar interaction contributions. PAFMPB is implemented in C and Fortran programming languages, with the Cilk Plus extension to harness the computing power of both multicore and vector processing. Computational experiments demonstrate the successful application of PAFMPB to the calculation of the PB potential on a dengue virus system with more than one million atoms and a mesh with approximately 20 million triangles.

  20. Ab initio molecular dynamics calculations of ion hydration free energies

    SciTech Connect

    Leung, Kevin; Rempe, Susan B.; Lilienfeld, O. Anatole von

    2009-05-28

    We apply ab initio molecular dynamics (AIMD) methods in conjunction with the thermodynamic integration or '{lambda}-path' technique to compute the intrinsic hydration free energies of Li{sup +}, Cl{sup -}, and Ag{sup +} ions. Using the Perdew-Burke-Ernzerhof functional, adapting methods developed for classical force field applications, and with consistent assumptions about surface potential ({phi}) contributions, we obtain absolute AIMD hydration free energies ({Delta}G{sub hyd}) within a few kcal/mol, or better than 4%, of Tissandier et al.'s [J. Phys. Chem. A 102, 7787 (1998)] experimental values augmented with the SPC/E water model {phi} predictions. The sums of Li{sup +}/Cl{sup -} and Ag{sup +}/Cl{sup -} AIMD {Delta}G{sub hyd}, which are not affected by surface potentials, are within 2.6% and 1.2 % of experimental values, respectively. We also report the free energy changes associated with the transition metal ion redox reaction Ag{sup +}+Ni{sup +}{yields}Ag+Ni{sup 2+} in water. The predictions for this reaction suggest that existing estimates of {Delta}G{sub hyd} for unstable radiolysis intermediates such as Ni{sup +} may need to be extensively revised.

  1. The metabolic energy cost of action potential velocity

    NASA Astrophysics Data System (ADS)

    Crotty, Patrick; Sangrey, Thomas; Levy, William

    2006-03-01

    Voltage changes in neurons and other active cells are caused by the passage of ions across the cell membrane. These ionic currents depend on the transmembrane ion concentration gradients, which in unmyelinated axons are maintained during rest and restored after electrical activity by an ATPase sodium-potassium exchanger in the membrane. The amount of ATP consumed by this exchanger can be taken as the metabolic energy cost of any electrical activity in the axon. We use this measure, along with biophysical models of voltage-gated sodium and potassium ion channels, to quantify the energy cost of action potentials propagating in squid giant axons. We find that the energy of an action potential can be naturally divided into three separate components associated with different aspects of the action potential. We calculate these energy components as functions of the ion channel densities and axon diameters and find that the component associated with the rising phase and velocity of the action potential achieves a minimum near the biological values of these parameters. This result, which is robust with respect to other parameters such as temperature, suggests that evolution has optimized the axon for the energy of the action potential wavefront.

  2. Nuclear momentum distribution and potential energy surface in hexagonal ice

    NASA Astrophysics Data System (ADS)

    Lin, Lin; Morrone, Joseph; Car, Roberto; Parrinello, Michele

    2011-03-01

    The proton momentum distribution in ice Ih has been recently measured by deep inelastic neutron scattering and calculated from open path integral Car-Parrinello simulation. Here we report a detailed investigation of the relation between momentum distribution and potential energy surface based on both experiment and simulation results. The potential experienced by the proton is largely harmonic and characterized by 3 principal frequencies, which can be associated to weighted averages of phonon frequencies via lattice dynamics calculations. This approach also allows us to examine the importance of quantum effects on the dynamics of the oxygen nuclei close to the melting temperature. Finally we quantify the anharmonicity that is present in the potential acting on the protons. This work is supported by NSF and by DOE.

  3. Potential energy surface of triplet N2O2

    NASA Astrophysics Data System (ADS)

    Varga, Zoltan; Meana-Pañeda, Rubén; Song, Guoliang; Paukku, Yuliya; Truhlar, Donald G.

    2016-01-01

    We present a global ground-state triplet potential energy surface for the N2O2 system that is suitable for treating high-energy vibrational-rotational energy transfer and collision-induced dissociation. The surface is based on multi-state complete-active-space second-order perturbation theory/minimally augmented correlation-consistent polarized valence triple-zeta electronic structure calculations plus dynamically scaled external correlation. In the multireference calculations, the active space has 14 electrons in 12 orbitals. The calculations cover nine arrangements corresponding to dissociative diatom-diatom collisions of N2, O2, and nitric oxide (NO), the interaction of a triatomic molecule (N2O and NO2) with the fourth atom, and the interaction of a diatomic molecule with a single atom (i.e., the triatomic subsystems). The global ground-state potential energy surface was obtained by fitting the many-body interaction to 54 889 electronic structure data points with a fitting function that is a permutationally invariant polynomial in terms of bond-order functions of the six interatomic distances.

  4. Potential energy surface of triplet N2O2.

    PubMed

    Varga, Zoltan; Meana-Pañeda, Rubén; Song, Guoliang; Paukku, Yuliya; Truhlar, Donald G

    2016-01-14

    We present a global ground-state triplet potential energy surface for the N2O2 system that is suitable for treating high-energy vibrational-rotational energy transfer and collision-induced dissociation. The surface is based on multi-state complete-active-space second-order perturbation theory/minimally augmented correlation-consistent polarized valence triple-zeta electronic structure calculations plus dynamically scaled external correlation. In the multireference calculations, the active space has 14 electrons in 12 orbitals. The calculations cover nine arrangements corresponding to dissociative diatom-diatom collisions of N2, O2, and nitric oxide (NO), the interaction of a triatomic molecule (N2O and NO2) with the fourth atom, and the interaction of a diatomic molecule with a single atom (i.e., the triatomic subsystems). The global ground-state potential energy surface was obtained by fitting the many-body interaction to 54 889 electronic structure data points with a fitting function that is a permutationally invariant polynomial in terms of bond-order functions of the six interatomic distances.

  5. Efficient calculation of relative binding free energies by umbrella sampling perturbation.

    PubMed

    Zeller, Fabian; Zacharias, Martin

    2014-12-01

    An important task of biomolecular simulation is the calculation of relative binding free energies upon chemical modification of partner molecules in a biomolecular complex. The potential of mean force (PMF) along a reaction coordinate for association or dissociation of the complex can be used to estimate binding affinities. A free energy perturbation approach, termed umbrella sampling (US) perturbation, has been designed that allows an efficient calculation of the change of the PMF upon modification of a binding partner based on the trajectories obtained for the wild type reference complex. The approach was tested on the interaction of modified water molecules in aqueous solution and applied to in silico alanine scanning of a peptide-protein complex. For the water interaction test case, excellent agreement with an explicit PMF calculation for each modification was obtained as long as no long range electrostatic perturbations were considered. For the alanine scanning, the experimentally determined ranking and binding affinity changes upon alanine substitutions could be reproduced within 0.1-2.0 kcal/mol. In addition, good agreement with explicitly calculated PMFs was obtained mostly within the sampling uncertainty. The combined US and perturbation approach yields, under the condition of sufficiently small system modifications, rigorously derived changes in free energy and is applicable to any PMF calculation.

  6. Metadyn View: Fast web-based viewer of free energy surfaces calculated by metadynamics

    NASA Astrophysics Data System (ADS)

    Hošek, Petr; Spiwok, Vojtěch

    2016-01-01

    Metadynamics is a highly successful enhanced sampling technique for simulation of molecular processes and prediction of their free energy surfaces. An in-depth analysis of data obtained by this method is as important as the simulation itself. Although there are several tools to compute free energy surfaces from metadynamics data, they usually lack user friendliness and a build-in visualization part. Here we introduce Metadyn View as a fast and user friendly viewer of bias potential/free energy surfaces calculated by metadynamics in Plumed package. It is based on modern web technologies including HTML5, JavaScript and Cascade Style Sheets (CSS). It can be used by visiting the web site and uploading a HILLS file. It calculates the bias potential/free energy surface on the client-side, so it can run online or offline without necessity to install additional web engines. Moreover, it includes tools for measurement of free energies and free energy differences and data/image export.

  7. A global potential energy surface for ArH2

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Walch, Stephen P.; Taylor, Peter R.

    1992-01-01

    We describe a simple analytic representation of the ArH2 potential energy surface which well reproduces the results of extensive ab initio electronic structure calculations. The analytic representation smoothly interpolates between the dissociated H2 and strong bonding limits. In the fitting process, emphasis is made on accurately reproducing regions of the potential expected to be important for high temperature (ca. 3000 K) collision processes. Overall, the anisotropy and H2 bond length dependence of the analytic representation well reproduce the input data.

  8. A global potential energy surface for ArH2

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Walch, Stephen P.; Taylor, Peter R.

    1993-01-01

    We describe a simple analytic representation of the ArH2 potential energy surface which well reproduces the results of extensive ab initio electronic structure calculations. The analytic representation smoothly interpolates between the dissociated H2 and strong bonding limits. In the fitting process, emphasis is made on accurately reproducing regions of the potential expected to be important for high temperature (ca. 3000 K) collision processes. Overall, the anisotropy and H2 bond length dependence of the analytic representation well reproduce the input data.

  9. The Potential for Energy Efficiency and Renewable Energy in North Carolina

    SciTech Connect

    Hadley, SW

    2003-08-06

    As many states have restructured their electric power industry, they have established a ''systems benefit charge'' to help fund those activities that will no longer be funded by utilities in the new structure. Examples include weatherization of low-income housing, efficiency programs, and renewable energy development. Varying amounts have been collected and allocated depending on state needs and abilities. One question that arises is what are the potential results of funding the different types of programs. What is the potential for energy efficiency or for renewable power, and what would be accomplished given the amount of funding that the system benefit charge may provide? The purpose of this project is to provide an initial estimate of the potential for energy efficiency and renewable energy in North Carolina. This potential could be funded by a public benefits fund resulting from a green power program being considered in the state. It concentrates on electric energy savings and production. Savings in buildings can include improvements to space conditioning as well as improvements to lighting or other appliances. Distributed power potential, through use of combined heat and power and renewables such as photovoltaic, wind, and biomass were examined. The goal is to provide information to decision makers who are developing a green power program in North Carolina. It will not be a complete and detailed study of all efficiency potentials but is more of a scoping exercise to determine the relative impacts and begin the process for a more definitive study at a later date. Statewide energy savings potential cannot be directly measured but must be calculated. First, the word ''potential'' means that the savings have not occurred yet. Second, the savings are often only indirectly measured by estimating what energy use there would have been without the changes in technology or behavior. Calculations through sampling and statistical analysis or by simulation are a necessary

  10. Calculation of electron affinities of polycyclic aromatic hydrocarbons and solvation energies of their radical anion.

    PubMed

    Betowski, Leon D; Enlow, Mark; Riddick, Lee; Aue, Donald H

    2006-11-30

    Electron affinities (EAs) and free energies for electron attachment (DeltaGo(a,298K)) have been directly calculated for 45 polynuclear aromatic hydrocarbons (PAHs) and related molecules by a variety of theoretical methods, with standard regression errors of about 0.07 eV (mean unsigned error = 0.05 eV) at the B3LYP/6-31 + G(d,p) level and larger errors with HF or MP2 methods or using Koopmans' Theorem. Comparison of gas-phase free energies with solution-phase reduction potentials provides a measure of solvation energy differences between the radical anion and neutral PAH. A simple Born-charging model approximates the solvation effects on the radical anions, leading to a good correlation with experimental solvation energy differences. This is used to estimate unknown or questionable EAs from reduction potentials. Two independent methods are used to predict DeltaGo(a,298K) values: (1) based upon DFT methods, or (2) based upon reduction potentials and the Born model. They suggest reassignments or a resolution of conflicting experimental EAs for nearly one-half (17 of 38) of the PAH molecules for which experimental EAs have been reported. For the antiaromatic molecules, 1,3,5-tri-tert-butylpentalene and the dithia-substituted cyclobutadiene 1, the reduction potentials lead to estimated EAs close to those expected from DFT calculations and provide a basis for the prediction of the EAs and reduction potentials of pentalene and cyclobutadiene. The Born model has been used to relate the electrostatic solvation energies of PAH and hydrocarbon radical anions, and spherical halide anions, alkali metal cations, and ammonium ions to effective ionic radii from DFT electron-density envelopes. The Born model used for PAHs has been successfully extended here to quantitatively explain the solvation energy of the C60 radical anion.

  11. INDIVIDUALISED CALCULATION OF TISSUE IMPARTED ENERGY IN BREAST TOMOSYNTHESIS.

    PubMed

    Geeraert, N; Klausz, R; Muller, S; Bloch, I; Bosmans, H

    2016-06-01

    The imparted energy to the glandular tissue in the breast (glandular imparted energy, GIE) is proposed for an improved assessment of the individual radiation-induced risk resulting from X-ray breast imaging. GIE is computed from an estimation of the quantity and localisation of glandular tissue in the breast. After a digital breast tomosynthesis (DBT) acquisition, the volumetric glandular content (volumetric breast density, VBD) is computed from the central X-ray projection. The glandular tissue distribution is determined by labelling the DBT voxels to ensure the conservation of the VBD. Finally, the GIE is calculated by Monte Carlo computation on the resulting tissue-labelled DBT volume. For verification, the method was applied to 10 breast-shaped digital phantoms made of different glandular spheres in an adipose background, and to a digital anthropomorphic phantom. Results were compared to direct GIE computations on the phantoms considered as 'ground-truth'. The major limitations in accuracy are those of DBT, in particular the limited z-resolution. However, for most phantoms, the results can be considered as acceptable.

  12. Prediction of Dyke Propagation using the Minimum Potential Energy Principle

    NASA Astrophysics Data System (ADS)

    Heimisson, Elías; Hooper, Andrew; Sigmundsson, Freysteinn

    2015-04-01

    An important aspect of eruption forecasting is the prediction and monitoring of dyke propagation. Eruptions occur where dykes propagate to the surface, with lava flows causing a major threat. When such eruption occur under ice, as is common in Iceland, they become explosive and often cause hazardous and destructive floods. Dykes have also been known to trigger explosive eruption when hot basaltic magma comes in contact with more developed volatile saturated magma. Such explosive eruptions pose a danger to both lives and property. At divergent plate boundaries new crust is formed primarily by dyke injections. These injections usually grow laterally away from a central volcano. Lateral growth of a dyke is expected to follow the minimum potential energy principle. Assuming a closed system, a dyke will tend to be emplaced such that it minimizes the total potential energy, ΦT, given by: ΦT = Φs + Φg (1) where Φs is the strain potential and Φg the gravitational energy potential. Assuming that the elastic medium behaves linearly the strain potential can be calculated by numerically integrating the strain energy density over a large volume. If the dyke is assumed to be propagating at a constant depth with respect to sea level the gravitational potential energy can be turned into a two dimensional integral. We do this by integrating the predicted vertical displacements multiplied by the local topographic load above a reference surface and the acceleration of gravity. We approximate strain and stress due to plate movements and then consider strain changes induced by the dyke formation. Opening of a dyke is energetically favourable when it releases strain energy built up at a divergent plate boundary, but once deviatoric stress in the crust adjacent to a segment is released it becomes favourable to propagate laterally. Dyke formation is associated with uplift on their flanks; the lower the topographic load over the flanks, the less energy it costs. For any given

  13. Improved methods for Feynman path integral calculations and their application to calculate converged vibrational–rotational partition functions, free energies, enthalpies, entropies, and heat capacities for methane

    SciTech Connect

    Mielke, Steven L. E-mail: truhlar@umn.edu; Truhlar, Donald G. E-mail: truhlar@umn.edu

    2015-01-28

    We present an improved version of our “path-by-path” enhanced same path extrapolation scheme for Feynman path integral (FPI) calculations that permits rapid convergence with discretization errors ranging from O(P{sup −6}) to O(P{sup −12}), where P is the number of path discretization points. We also present two extensions of our importance sampling and stratified sampling schemes for calculating vibrational–rotational partition functions by the FPI method. The first is the use of importance functions for dihedral angles between sets of generalized Jacobi coordinate vectors. The second is an extension of our stratification scheme to allow some strata to be defined based only on coordinate information while other strata are defined based on both the geometry and the energy of the centroid of the Feynman path. These enhanced methods are applied to calculate converged partition functions by FPI methods, and these results are compared to ones obtained earlier by vibrational configuration interaction (VCI) calculations, both calculations being for the Jordan–Gilbert potential energy surface. The earlier VCI calculations are found to agree well (within ∼1.5%) with the new benchmarks. The FPI partition functions presented here are estimated to be converged to within a 2σ statistical uncertainty of between 0.04% and 0.07% for the given potential energy surface for temperatures in the range 300–3000 K and are the most accurately converged partition functions for a given potential energy surface for any molecule with five or more atoms. We also tabulate free energies, enthalpies, entropies, and heat capacities.

  14. Improved methods for Feynman path integral calculations and their application to calculate converged vibrational-rotational partition functions, free energies, enthalpies, entropies, and heat capacities for methane.

    PubMed

    Mielke, Steven L; Truhlar, Donald G

    2015-01-28

    We present an improved version of our "path-by-path" enhanced same path extrapolation scheme for Feynman path integral (FPI) calculations that permits rapid convergence with discretization errors ranging from O(P(-6)) to O(P(-12)), where P is the number of path discretization points. We also present two extensions of our importance sampling and stratified sampling schemes for calculating vibrational-rotational partition functions by the FPI method. The first is the use of importance functions for dihedral angles between sets of generalized Jacobi coordinate vectors. The second is an extension of our stratification scheme to allow some strata to be defined based only on coordinate information while other strata are defined based on both the geometry and the energy of the centroid of the Feynman path. These enhanced methods are applied to calculate converged partition functions by FPI methods, and these results are compared to ones obtained earlier by vibrational configuration interaction (VCI) calculations, both calculations being for the Jordan-Gilbert potential energy surface. The earlier VCI calculations are found to agree well (within ∼1.5%) with the new benchmarks. The FPI partition functions presented here are estimated to be converged to within a 2σ statistical uncertainty of between 0.04% and 0.07% for the given potential energy surface for temperatures in the range 300-3000 K and are the most accurately converged partition functions for a given potential energy surface for any molecule with five or more atoms. We also tabulate free energies, enthalpies, entropies, and heat capacities.

  15. Improved methods for Feynman path integral calculations and their application to calculate converged vibrational-rotational partition functions, free energies, enthalpies, entropies, and heat capacities for methane.

    PubMed

    Mielke, Steven L; Truhlar, Donald G

    2015-01-28

    We present an improved version of our "path-by-path" enhanced same path extrapolation scheme for Feynman path integral (FPI) calculations that permits rapid convergence with discretization errors ranging from O(P(-6)) to O(P(-12)), where P is the number of path discretization points. We also present two extensions of our importance sampling and stratified sampling schemes for calculating vibrational-rotational partition functions by the FPI method. The first is the use of importance functions for dihedral angles between sets of generalized Jacobi coordinate vectors. The second is an extension of our stratification scheme to allow some strata to be defined based only on coordinate information while other strata are defined based on both the geometry and the energy of the centroid of the Feynman path. These enhanced methods are applied to calculate converged partition functions by FPI methods, and these results are compared to ones obtained earlier by vibrational configuration interaction (VCI) calculations, both calculations being for the Jordan-Gilbert potential energy surface. The earlier VCI calculations are found to agree well (within ∼1.5%) with the new benchmarks. The FPI partition functions presented here are estimated to be converged to within a 2σ statistical uncertainty of between 0.04% and 0.07% for the given potential energy surface for temperatures in the range 300-3000 K and are the most accurately converged partition functions for a given potential energy surface for any molecule with five or more atoms. We also tabulate free energies, enthalpies, entropies, and heat capacities. PMID:25637967

  16. Novel mixture model for the representation of potential energy surfaces

    NASA Astrophysics Data System (ADS)

    Pham, Tien Lam; Kino, Hiori; Terakura, Kiyoyuki; Miyake, Takashi; Dam, Hieu Chi

    2016-10-01

    We demonstrate that knowledge of chemical physics on a materials system can be automatically extracted from first-principles calculations using a data mining technique; this information can then be utilized to construct a simple empirical atomic potential model. By using unsupervised learning of the generative Gaussian mixture model, physically meaningful patterns of atomic local chemical environments can be detected automatically. Based on the obtained information regarding these atomic patterns, we propose a chemical-structure-dependent linear mixture model for estimating the atomic potential energy. Our experiments show that the proposed mixture model significantly improves the accuracy of the prediction of the potential energy surface for complex systems that possess a large diversity in their local structures.

  17. An efficient method for energy levels calculation using full symmetry and exact kinetic energy operator: Tetrahedral molecules

    SciTech Connect

    Nikitin, A. V.; Rey, M.; Tyuterev, Vl. G.

    2015-03-07

    A simultaneous use of the full molecular symmetry and of an exact kinetic energy operator (KEO) is of key importance for accurate predictions of vibrational levels at a high energy range from a potential energy surface (PES). An efficient method that permits a fast convergence of variational calculations would allow iterative optimization of the PES parameters using experimental data. In this work, we propose such a method applied to tetrahedral AB{sub 4} molecules for which a use of high symmetry is crucial for vibrational calculations. A symmetry-adapted contracted angular basis set for six redundant angles is introduced. Simple formulas using this basis set for explicit calculation of the angular matrix elements of KEO and PES are reported. The symmetric form (six redundant angles) of vibrational KEO without the sin(q){sup −2} type singularity is derived. The efficient recursive algorithm based on the tensorial formalism is used for the calculation of vibrational matrix elements. A good basis set convergence for the calculations of vibrational levels of the CH{sub 4} molecule is demonstrated.

  18. PSOLV: a code for calculating the potentials and densities in MFTF-B

    SciTech Connect

    Colborn, J.A.

    1983-08-17

    Code PSOLV solves for potential and densities at the cardinal points of MFTF-B. The code is equipped to handle both the throttle-coil and the axicell geometries. For the throttle-coil case, the potential at point MXO is input, while the potentials and densities at points MAI, b, and A are calculated. For the axicell case, the code must additionally solve for the potentials and densities at points X and MXO. PSOLV is intended primarily for use as a subroutine in TREQ, a code being developed by Rensink that calculates the densities and potentials at the cardinal points of MFTF-B as a function of time. TREQ is to be used for modeling start-up behavior.

  19. Molecular wave function and effective adiabatic potentials calculated by extended multi-configuration time-dependent Hartree-Fock method

    SciTech Connect

    Kato, Tsuyoshi; Ide, Yoshihiro; Yamanouchi, Kaoru

    2015-12-31

    We first calculate the ground-state molecular wave function of 1D model H{sub 2} molecule by solving the coupled equations of motion formulated in the extended multi-configuration time-dependent Hartree-Fock (MCTDHF) method by the imaginary time propagation. From the comparisons with the results obtained by the Born-Huang (BH) expansion method as well as with the exact wave function, we observe that the memory size required in the extended MCTDHF method is about two orders of magnitude smaller than in the BH expansion method to achieve the same accuracy for the total energy. Second, in order to provide a theoretical means to understand dynamical behavior of the wave function, we propose to define effective adiabatic potential functions and compare them with the conventional adiabatic electronic potentials, although the notion of the adiabatic potentials is not used in the extended MCTDHF approach. From the comparison, we conclude that by calculating the effective potentials we may be able to predict the energy differences among electronic states even for a time-dependent system, e.g., time-dependent excitation energies, which would be difficult to be estimated within the BH expansion approach.

  20. Potential energy hypersurface and molecular flexibility

    NASA Astrophysics Data System (ADS)

    Koča, Jaroslav

    1993-02-01

    The molecular flexibility phenomenon is discussed from the conformational potential energy(hyper) surface (PES) point of view. Flexibility is considered as a product of three terms: thermodynamic, kinetic and geometrical. Several expressions characterizing absolute and relative molecular flexibility are introduced, depending on a subspace studied of the entire conformational space, energy level E of PES as well as absolute temperature. Results obtained by programs DAISY, CICADA and PANIC in conjunction with molecular mechanics program MMX for flexibility analysis of isopentane, 2,2-dimethylpentane and isohexane molecules are introduced.

  1. Sparse representation for a potential energy surface

    NASA Astrophysics Data System (ADS)

    Seko, Atsuto; Takahashi, Akira; Tanaka, Isao

    2014-07-01

    We propose a simple scheme to estimate the potential energy surface (PES) for which the accuracy can be easily controlled and improved. It is based on model selection within the framework of linear regression using the least absolute shrinkage and selection operator (LASSO) technique. Basis functions are selected from a systematic large set of candidate functions. The sparsity of the PES significantly reduces the computational cost of evaluating the energy and force in molecular dynamics simulations without losing accuracy. The usefulness of the scheme for describing the elemental metals Na and Mg is clearly demonstrated.

  2. The molecular potential energy surface and vibrational energy levels of methyl fluoride. Part II.

    PubMed

    Manson, Steven A; Law, Mark M; Atkinson, Ian A; Thomson, Grant A

    2006-06-28

    New analytical bending and stretching, ground electronic state, potential energy surfaces for CH(3)F are reported. The surfaces are expressed in bond-length, bond-angle internal coordinates. The four-dimensional stretching surface is an accurate, least squares fit to over 2000 symmetrically unique ab initio points calculated at the CCSD(T) level. Similarly, the five-dimensional bending surface is a fit to over 1200 symmetrically unique ab initio points. This is an important first stage towards a full nine-dimensional potential energy surface for the prototype CH(3)F molecule. Using these surfaces, highly excited stretching and (separately) bending vibrational energy levels of CH(3)F are calculated variationally using a finite basis representation method. The method uses the exact vibrational kinetic energy operator derived for XY(3)Z systems by Manson and Law (preceding paper, Part I, Phys. Chem. Chem. Phys., 2006, 8, DOI: 10.1039/b603106d). We use the full C(3v) symmetry and the computer codes are designed to use an arbitrary potential energy function. Ultimately, these results will be used to design a compact basis for fully coupled stretch-bend calculations of the vibrational energy levels of the CH(3)F system.

  3. Density functional theory calculations of the redox potentials of actinide(VI)/actinide(V) couple in water.

    PubMed

    Steele, Helen M; Guillaumont, Dominique; Moisy, Philippe

    2013-05-30

    The measured redox potential of an actinide at an electrode surface involves the transfer of a single electron from the electrode surface on to the actinide center. Before electron transfer takes place, the complexing ligands and molecules of solvation need to become structurally arranged such that the electron transfer is at its most favorable. Following the electron transfer, there is further rearrangement to obtain the minimum energy structure for the reduced state. As such, there are three parts to the total energy cycle required to take the complex from its ground state oxidized form to its ground state reduced form. The first part of the energy comes from the structural rearrangement and solvation energies of the actinide species before the electron transfer or charge transfer process; the second part, the energy of the electron transfer; the third part, the energy required to reorganize the ligands and molecules of solvation around the reduced species. The time resolution of electrochemical techniques such as cyclic voltammetry is inadequate to determine to what extent bond and solvation rearrangement occurs before or after electron transfer; only for a couple to be classed as reversible is it fast in terms of the experimental time. Consequently, the partitioning of the energy theoretically is of importance to obtain good experimental agreement. Here we investigate the magnitude of the instantaneous charge transfer through calculating the fast one electron reduction energies of AnO2(H2O)n(2+), where An = U, Np, and Pu, for n = 4-6, in solution without inclusion of the structural optimization energy of the reduced form. These calculations have been performed using a number of DFT functionals, including the recently developed functionals of Zhao and Truhlar. The results obtained for calculated electron affinities in the aqueous phase for the AnO2(H2O)5(2+/+) couples are within 0.04 V of accepted experimental redox potentials, nearly an order of magnitude

  4. Calculation of the polarization potential for e-N2 collisions

    NASA Technical Reports Server (NTRS)

    Onda, K.; Temkin, A.

    1983-01-01

    A polarization potential V(pol) for e-N2 collisions is calculated by the generalization of the static part of the method of polarized orbitals to molecular targets. Partial differential equations (PDE) are derived for polarized orbitals, which are functions of the distance (r) from the molecular center and angle (theta) from the molecular axis. The equations are solved with the use of the noniterative PDE technique. From the polarized orbitals a polarization potential can be constructed whose r and theta dependence is found to be significantly different from the well-known phenomenological one. The two potentials are further compared by carrying out limited hybrid-theory scattering calculations. Only those scattering results based on the calculated V(pol) are in satisfactory accord with experiment.

  5. Free molecular collision cross section calculation methods for nanoparticles and complex ions with energy accommodation

    SciTech Connect

    Larriba, Carlos Hogan, Christopher J.

    2013-10-15

    The structures of nanoparticles, macromolecules, and molecular clusters in gas phase environments are often studied via measurement of collision cross sections. To directly compare structure models to measurements, it is hence necessary to have computational techniques available to calculate the collision cross sections of structural models under conditions matching measurements. However, presently available collision cross section methods contain the underlying assumption that collision between gas molecules and structures are completely elastic (gas molecule translational energy conserving) and specular, while experimental evidence suggests that in the most commonly used background gases for measurements, air and molecular nitrogen, gas molecule reemission is largely inelastic (with exchange of energy between vibrational, rotational, and translational modes) and should be treated as diffuse in computations with fixed structural models. In this work, we describe computational techniques to predict the free molecular collision cross sections for fixed structural models of gas phase entities where inelastic and non-specular gas molecule reemission rules can be invoked, and the long range ion-induced dipole (polarization) potential between gas molecules and a charged entity can be considered. Specifically, two calculation procedures are described detail: a diffuse hard sphere scattering (DHSS) method, in which structures are modeled as hard spheres and collision cross sections are calculated for rectilinear trajectories of gas molecules, and a diffuse trajectory method (DTM), in which the assumption of rectilinear trajectories is relaxed and the ion-induced dipole potential is considered. Collision cross section calculations using the DHSS and DTM methods are performed on spheres, models of quasifractal aggregates of varying fractal dimension, and fullerene like structures. Techniques to accelerate DTM calculations by assessing the contribution of grazing gas

  6. Linearity condition for orbital energies in density functional theory (V): Extension to excited state calculations

    NASA Astrophysics Data System (ADS)

    Imamura, Yutaka; Suzuki, Kensei; Iizuka, Takeshi; Nakai, Hiromi

    2015-01-01

    A new scheme is proposed for constructing an orbital-specific (OS) exchange-correlation functional that satisfies multiple linearity conditions for orbital energies (LCOEs). The Hartree-Fock exchange portions in the OS exchange-correlation functional, based on a multiply range-separated functional, are set so as to satisfy the multiple LCOEs. The current scheme has also been extended to calculations of core, valence, and Rydberg excitations. Numerical assessments on ionization potentials, electron affinities and excitation energies have confirmed accurate descriptions of core, valence, and Rydberg orbitals by the OS hybrid functional.

  7. Volume 1: Calculating potential to emit releases and doses for FEMP's and NOCs

    SciTech Connect

    HILL, J.S.

    1999-07-27

    The purpose of this document is to provide Hanford Site facilities a handbook for estimating potential emissions and the subsequent offsite doses. General guidelines and information are provided to assist personnel in estimating emissions for use with U.S. Department of Energy (DOE) facility effluent monitoring plans (FEMPs) and regulatory notices of construction (NOCs), per 40 Code of Federal Regulations (CFR) Part 61, Subpart H, and Washington Administrative Code (WAC) Chapter 246-247 requirements. This document replaces Unit Dose Calculation Methods and Summary of Facility Effluent Monitoring Plan Determinations (WHC-EP-0498). Meteorological data from 1983 through 1996, 13-year data set, was used to develop the unit dose factors provided by this document, with the exception of two meteorological stations. Meteorological stations 23 and 24, located at Gable Mountain and the 100-F Area, only have data from 1986 through 1996, 10-year data set. The scope of this document includes the following: Estimating emissions and resulting effective dose equivalents (EDE) to a facility's nearest offsite receptor (NOR) for use with NOCs under 40 CFR Part 61, Subpart H, requirements Estimating emissions and resulting EDEs to a facility's or emission unit's NOR for use with NOCs under the WAC Chapter 246-247 requirements Estimating emissions and resulting EDEs to a facility's or emission unit's NOR for use with FEMPs and FEMP determinations under DOE Orders 5400.1 and 5400.5 requirements.

  8. A calculation of the diffusion energies for adatoms on surfaces of F.C.C. metals

    NASA Technical Reports Server (NTRS)

    Halicioglu, T.; Pound, G. M.

    1979-01-01

    The activation energies for diffusion were determined for gold, platinum and iridium adatoms on plane and plane PT surfaces and were found to be in good agreement with the measurements reported by Bassett and Webber. The Lennard-Jones pair potentials were used to model the interatomic forces, and relaxation of the substrate atoms in near proximity to the adatom was considered in detail. The present calculations clarify the mechanism of the observed two-dimensional diffusion of platinum and iridium atoms on a plane PT surface. The results are compared with those obtained using Morse potential functions and different relaxation techniques.

  9. The Potential For Energy Efficiency In The State of Iowa

    SciTech Connect

    Hadley, SW

    2001-12-05

    The purpose of this study was to do an initial estimate of the potential for energy savings in the state of Iowa. Several methods for determining savings were examined, including existing programs, surveys, savings calculators, and economic simulation. Each method has advantages and disadvantages, trading off between detail of information, accuracy of results, and scope. This paper concentrated on using economic simulation (the NEMS model (EIA 2000a)) to determine market potential for energy savings for the residential and commercial sectors. The results of surveys were used to calculate the economic potential for savings in the industrial sector. The NEMS model is used by the Energy Information Administration to calculate twenty-year projections of energy use for every region of the country. The results of the Annual Energy Outlook 2000 were used as the Base case (EIA 1999a). Two alternative cases were created to simulate energy savings policies. Voluntary, market-related programs were simulated by lowering the effective discount rates that end-users use when making decisions on equipment purchases. Standards programs in the residential sector were simulated by eliminating the availability of low efficiency equipment in future years. The parameters for these programs were based on the Moderate scenario from the DOE Clean Energy Futures study (Interlaboratory Working Group 2000), which assumed increased concern by society on energy efficiency but not to the point of fiscal policies such as taxes or direct subsidies. The study only considered a subset of the various programs, policies, and technologies that could reduce energy use. The major end-uses in the residential sector affected by the policies were space cooling (20% savings by 2020) and water heating (14% savings by 2020.) Figure S-1 shows the space cooling savings when voluntary programs and minimum efficiency standards were implemented. Refrigerators, freezers, and clothes dryers saw slight improvements

  10. Computed potential energy surfaces for chemical reactions

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    1990-01-01

    The objective was to obtain accurate potential energy surfaces (PES's) for a number of reactions which are important in the H/N/O combustion process. The interest in this is centered around the design of the SCRAM jet engine for the National Aerospace Plane (NASP), which was envisioned as an air-breathing hydrogen-burning vehicle capable of reaching velocities as large as Mach 25. Preliminary studies indicated that the supersonic flow in the combustor region of the scram jet engine required accurate reaction rate data for reactions in the H/N/O system, some of which was not readily available from experiment. The most important class of combustion reactions from the standpoint of the NASP project are radical recombinaton reactions, since these reactions result in most of the heat release in the combustion process. Theoretical characterizations of the potential energy surfaces for these reactions are presented and discussed.

  11. Accuracy of Effective Core Potentials and Basis Sets for Density Functional Calculations, Including Relativistic Effects, As Illustrated by Calculations on Arsenic Compounds.

    PubMed

    Xu, Xuefei; Truhlar, Donald G

    2011-09-13

    For molecules containing the fourth-period element arsenic, we test (i, ii) the accuracy of all-electron (AE) basis sets from the def2-xZVP and ma-xZVP series (where xZ is S, TZ, or QZ), (iii) the accuracy of the 6-311G series of AE basis sets with additional polarization and diffuse functions, and (iv) the performance of effective core potentials (ECPs). The first set of tests involves basis-set convergence studies with eleven density functionals for five cases: equilibrium dissociation energy (De) of As2, vertical ionization potential (VIP) of As2, IP of As, acid dissociation of H3AsO4, and De of FeAs. A second set of tests involves the same kinds of basis-set convergence studies for the VIP and De values of As3 and As4 clusters. Both relativistic and nonrelativistic calculations are considered, including in each case both AE calculations and calculations with ECPs. Convergence and accuracy are assessed by comparing to relativistic AE calculations with the cc-pV5Z-DK or ma-cc-pV5Z-DK basis and to nonrelativistic AE calculations with the cc-pV5Z or ma-cc-pV5Z basis. The primary objective of this study is to evaluate the abilities of ECPs with both their recommended basis sets and other basis sets to reproduce the results of all-electron relativistic calculations. The performance of the def2 and ma series basis sets is consistent with their sizes, and quadruple-ζ basis sets are the best. The def2-TZVP basis set performs better than most of the 6-311G series basis sets, which are the most commonly used basis sets in the previous studies of arsenic compounds. However, relativistic def2-TZVP calculations are not recommended. The large-core ECPs, which are the only available ECPs for arsenic in the popular Gaussian program, have average errors of 9-12 kcal/mol for the arsenic systems studied; therefore, these ECPs are not recommended. The triple-ζ small-core relativistic ECP (RECP) basis set cc-pVTZ-PP is found to have performance better than that of the def2-TZVP

  12. Energy Savings Potential of Radiative Cooling Technologies

    SciTech Connect

    Fernandez, Nicholas; Wang, Weimin; Alvine, Kyle J.; Katipamula, Srinivas

    2015-11-30

    Pacific Northwest National Laboratory (PNNL), with funding from the U.S. Department of Energy’s (DOE’s) Building Technologies Program (BTP), conducted a study to estimate, through simulation, the potential cooling energy savings that could be achieved through novel approaches to capturing free radiative cooling in buildings, particularly photonic ‘selective emittance’ materials. This report documents the results of that study.

  13. Potential energy surfaces and reaction dynamics of polyatomic molecules

    SciTech Connect

    Chang, Yan-Tyng.

    1991-11-01

    A simple empirical valence bond (EVB) model approach is suggested for constructing global potential energy surfaces for reactions of polyatomic molecular systems. This approach produces smooth and continuous potential surfaces which can be directly utilized in a dynamical study. Two types of reactions are of special interest, the unimolecular dissociation and the unimolecular isomerization. For the first type, the molecular dissociation dynamics of formaldehyde on the ground electronic surface is investigated through classical trajectory calculations on EVB surfaces. The product state distributions and vector correlations obtained from this study suggest very similar behaviors seen in the experiments. The intramolecular hydrogen atom transfer in the formic acid dimer is an example of the isomerization reaction. High level ab initio quantum chemistry calculations are performed to obtain optimized equilibrium and transition state dimer geometries and also the harmonic frequencies.

  14. Global Expression for Representing Diatomic Potential-Energy Curves

    NASA Technical Reports Server (NTRS)

    Ferrante, John; Schlosser, Herbert; Smith, John R.

    1991-01-01

    A three-parameter expression that gives an accurate fit to diatomic potential curves over the entire range of separation for charge transfers between 0 and 1. It is based on a generalization of the universal binding-energy relation of Smith et al. (1989) with a modification that describes the crossover from a partially ionic state to the neutral state at large separations. The expression is tested by comparison with first-principles calculations of the potential curves ranging from covalently bonded to ionically bonded. The expression is also used to calculate spectroscopic constants form a curve fit to the first-principles curves. A comparison is made with experimental values of the spectroscopic constants.

  15. 5 CFR 591.220 - How does OPM calculate energy utility cost indexes?

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 5 Administrative Personnel 1 2010-01-01 2010-01-01 false How does OPM calculate energy utility... Areas Cost-Of-Living Allowances § 591.220 How does OPM calculate energy utility cost indexes? (a) OPM calculates energy utility cost indexes based on the relative cost of maintaining a standard size dwelling...

  16. Identification of HIV Inhibitors Guided by Free Energy Perturbation Calculations

    PubMed Central

    Acevedo, Orlando; Ambrose, Zandrea; Flaherty, Patrick T.; Aamer, Hadega; Jain, Prashi; Sambasivarao, Somisetti V.

    2013-01-01

    Free energy perturbation (FEP) theory coupled to molecular dynamics (MD) or Monte Carlo (MC) statistical mechanics offers a theoretically precise method for determining the free energy differences of related biological inhibitors. Traditionally requiring extensive computational resources and expertise, it is only recently that its impact is being felt in drug discovery. A review of computer-aided anti-HIV efforts employing FEP calculations is provided here that describes early and recent successes in the design of human immunodeficiency virus type 1 (HIV-1) protease and non-nucleoside reverse transcriptase inhibitors. In addition, our ongoing work developing and optimizing leads for small molecule inhibitors of cyclophilin A (CypA) is highlighted as an update on the current capabilities of the field. CypA has been shown to aid HIV-1 replication by catalyzing the cis/trans isomerization of a conserved Gly-Pro motif in the N-terminal domain of HIV-1 capsid (CA) protein. In the absence of a functional CypA, e.g., by the addition of an inhibitor such as cyclosporine A (CsA), HIV-1 has reduced infectivity. Our simulations of acylurea-based and 1-indanylketone-based CypA inhibitors have determined that their nanomolar and micromolar binding affinities, respectively, are tied to their ability to stabilize Arg55 and Asn102. A structurally novel 1-(2,6-dichlorobenzamido) indole core was proposed to maximize these interactions. FEP-guided optimization, experimental synthesis, and biological testing of lead compounds for toxicity and inhibition of wild-type HIV-1 and CA mutants have demonstrated a dose-dependent inhibition of HIV-1 infection in two cell lines. While the inhibition is modest compared to CsA, the results are encouraging. PMID:22316150

  17. NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS (NESHAP) SUBPART H RADIONUCLIDES POTENTIAL TO EMIT CALCULATIONS

    SciTech Connect

    EARLEY JN

    2008-07-23

    This document provides an update of the status of stacks on the Hanford Site and the potential radionuclide emissions, i.e., emissions that could occur with no control devices in place. This review shows the calculations that determined whether the total effective dose equivalent (TEDE) received by the maximum public receptor as a result of potential emissions from any one of these stacks would exceed 0.1 millirem/year. Such stacks require continuous monitoring of the effluent, or other monitoring, to meet the requirements of Washington Administrative code (WAC) 246-247-035(1)(a)(ii) and WAC 246-247-075(1), -(2), and -(6). This revised update reviews the potential-to-emit (PTE) calculations of 31 stacks for Fluor Hanford, Inc. Of those 31 stacks, 11 have the potential to cause a TEDE greater than 0.1 mrem/year.

  18. Free energy calculations, enhanced by a Gaussian ansatz, for the "chemical work" distribution.

    PubMed

    Boulougouris, Georgios C

    2014-05-15

    The evaluation of the free energy is essential in molecular simulation because it is intimately related with the existence of multiphase equilibrium. Recently, it was demonstrated that it is possible to evaluate the Helmholtz free energy using a single statistical ensemble along an entire isotherm by accounting for the "chemical work" of transforming each molecule, from an interacting one, to an ideal gas. In this work, we show that it is possible to perform such a free energy perturbation over a liquid vapor phase transition. Furthermore, we investigate the link between a general free energy perturbation scheme and the novel nonequilibrium theories of Crook's and Jarzinsky. We find that for finite systems away from the thermodynamic limit the second law of thermodynamics will always be an inequality for isothermal free energy perturbations, resulting always to a dissipated work that may tend to zero only in the thermodynamic limit. The work, the heat, and the entropy produced during a thermodynamic free energy perturbation can be viewed in the context of the Crooks and Jarzinsky formalism, revealing that for a given value of the ensemble average of the "irreversible" work, the minimum entropy production corresponded to a Gaussian distribution for the histogram of the work. We propose the evaluation of the free energy difference in any free energy perturbation based scheme on the average irreversible "chemical work" minus the dissipated work that can be calculated from the variance of the distribution of the logarithm of the work histogram, within the Gaussian approximation. As a consequence, using the Gaussian ansatz for the distribution of the "chemical work," accurate estimates for the chemical potential and the free energy of the system can be performed using much shorter simulations and avoiding the necessity of sampling the computational costly tails of the "chemical work." For a more general free energy perturbation scheme that the Gaussian ansatz may not be

  19. Al(fcc):Al{sub 3}Sc(L1{sub 2}) interphase boundary energy calculations

    SciTech Connect

    Hyland, R.W. Jr.; Rohrer, C.L.; Asta, M.; Foiles, S.M.

    1998-06-12

    These calculations assess the applicability of classical nucleation theory to the reaction f.c.c. {r_arrow} L1{sub 2} occurring in dilute Al-Sc alloys. The orientation and temperature dependence of the energies of coherent Al(f.c.c.):Al{sub 3}Sc(L1{sub 2}) interphase boundaries were studied using atomistic simulation and a low temperature expansion (LTE) of the grand potential. Embedded atom method potentials were developed for both sets of calculations. Atomistic 0 K results for the anisotropy of the interphase boundary enthalpy gave {gamma}{sub (100)} < {gamma}{sub (110)} < {gamma}{sub (111)} with values of 32.5, 51.3, and 66.3 mJ/m{sup 2}, respectively. LTE calculations of the excess grand potential of the (100) interface predicted a nearly temperature independent interfacial energy below 400 K that decreased modestly above 400 K. Monte Carlo (MC) simulations produced a compositional diffuseness of about 4 atomic layers separating the two bulk phases. Because the spatial extent of this region is very similar to the classically determined critical nucleus dimensions extracted from nucleation rate data, it is concluded that critical nuclei of Al{sub 3}Sc are most likely of nonclassical design at high undercooling.

  20. A finite volume method for calculating transonic potential flow around wings from the pressure minimum integral

    NASA Technical Reports Server (NTRS)

    Eberle, A.

    1978-01-01

    Analysis of the pressure minimum integral in the calculation of three-dimensional potential flow around wings makes it possible to use non-rectangular mesh networks for distributing the three-dimensional potential into discrete points. The method is comparatively easily expanded to the treatment of realistic airplane configurations. Shock-pressure affected pressure distributions on any wings are determined with accuracy using this method.

  1. EnergyPlus Analysis Capabilities for Use in California Building Energy Efficiency Standards Development and Compliance Calculations

    SciTech Connect

    Hong, Tianzhen; Buhl, Fred; Haves, Philip

    2008-03-28

    California has been using DOE-2 as the main building energy analysis tool in the development of building energy efficiency standards (Title 24) and the code compliance calculations. However, DOE-2.1E is a mature program that is no longer supported by LBNL on contract to the USDOE, or by any other public or private entity. With no more significant updates in the modeling capabilities of DOE-2.1E during recent years, DOE-2.1E lacks the ability to model, with the necessary accuracy, a number of building technologies that have the potential to reduce significantly the energy consumption of buildings in California. DOE-2's legacy software code makes it difficult and time consuming to add new or enhance existing modeling features in DOE-2. Therefore the USDOE proposed to develop a new tool, EnergyPlus, which is intended to replace DOE-2 as the next generation building simulation tool. EnergyPlus inherited most of the useful features from DOE-2 and BLAST, and more significantly added new modeling capabilities far beyond DOE-2, BLAST, and other simulations tools currently available. With California's net zero energy goals for new residential buildings in 2020 and for new commercial buildings in 2030, California needs to evaluate and promote currently available best practice and emerging technologies to significantly reduce energy use of buildings for space cooling and heating, ventilating, refrigerating, lighting, and water heating. The California Energy Commission (CEC) needs to adopt a new building energy simulation program for developing and maintaining future versions of Title 24. Therefore, EnergyPlus became a good candidate to CEC for its use in developing and complying with future Title 24 upgrades. In 2004, the Pacific Gas and Electric Company contracted with ArchitecturalEnergy Corporation (AEC), Taylor Engineering, and GARD Analytics to evaluate EnergyPlus in its ability to model those energy efficiency measures specified in both the residential and

  2. Calculating activation energies for temperature compensation in circadian rhythms

    NASA Astrophysics Data System (ADS)

    Bodenstein, C.; Heiland, I.; Schuster, S.

    2011-10-01

    Many biological species possess a circadian clock, which helps them anticipate daily variations in the environment. In the absence of external stimuli, the rhythm persists autonomously with a period of approximately 24 h. However, single pulses of light, nutrients, chemicals or temperature can shift the clock phase. In the case of light- and temperature-cycles, this allows entrainment of the clock to cycles of exactly 24 h. Circadian clocks have the remarkable property of temperature compensation, that is, the period of the circadian rhythm remains relatively constant within a physiological range of temperatures. For several organisms, temperature-regulated processes within the circadian clock have been identified in recent years. However, how these processes contribute to temperature compensation is not fully understood. Here, we theoretically investigate temperature compensation in general oscillatory systems. It is known that every oscillator can be locally temperature compensated around a reference temperature, if reactions are appropriately balanced. A balancing is always possible if the control coefficient with respect to the oscillation period of at least one reaction in the oscillator network is positive. However, for global temperature compensation, the whole physiological temperature range is relevant. Here, we use an approach which leads to an optimization problem subject to the local balancing principle. We use this approach to analyse different circadian clock models proposed in the literature and calculate activation energies that lead to temperature compensation.

  3. Free Energy Calculations using a Swarm-Enhanced Sampling Molecular Dynamics Approach.

    PubMed

    Burusco, Kepa K; Bruce, Neil J; Alibay, Irfan; Bryce, Richard A

    2015-10-26

    Free energy simulations are an established computational tool in modelling chemical change in the condensed phase. However, sampling of kinetically distinct substates remains a challenge to these approaches. As a route to addressing this, we link the methods of thermodynamic integration (TI) and swarm-enhanced sampling molecular dynamics (sesMD), where simulation replicas interact cooperatively to aid transitions over energy barriers. We illustrate the approach by using alchemical alkane transformations in solution, comparing them with the multiple independent trajectory TI (IT-TI) method. Free energy changes for transitions computed by using IT-TI grew increasingly inaccurate as the intramolecular barrier was heightened. By contrast, swarm-enhanced sampling TI (sesTI) calculations showed clear improvements in sampling efficiency, leading to more accurate computed free energy differences, even in the case of the highest barrier height. The sesTI approach, therefore, has potential in addressing chemical change in systems where conformations exist in slow exchange.

  4. Fully Relativistic Full-Potential Calculations of Magnetic Moments in Uranium Monochalcogenides with the Dirac Current

    NASA Astrophysics Data System (ADS)

    Shugo Suzuki,; Hidehisa Ohta,

    2010-07-01

    We study the orbital, spin, and total magnetic moments in uranium monochalcogenides, UX where X=S, Se, and Te, using the fully relativistic full-potential calculations based on the spin density functional theory. In particular, the orbital magnetic moments are calculated with the Dirac current. We employ two methods which adopt distinctly different basis sets; one is the fully relativistic full-potential linear-combination-of-atomic-orbitals (FFLCAO) method and the other is the fully relativistic full-potential mixed-basis (FFMB) method. Showing that the orbital magnetic moments calculated using the FFLCAO method and those calculated using the FFMB method agree very well with each other, we demonstrate that, in contrast to the conventional method, the method with the Dirac current enables us to calculate the orbital magnetic moments even if the basis set includes basis functions with no definite angular momenta, e.g., the plane waves in the FFMB method. Furthermore, it is found that the orbital magnetic moments obtained in this work are larger by nearly 0.4 μB than those obtained using the conventional method. This is crucial because the resultant differences in the total magnetic moments are about 30%. We compare the results of this work with those of previous theoretical and experimental studies.

  5. Precise calculations in simulations of the interaction of low energy neutrons with nano-dispersed media

    NASA Astrophysics Data System (ADS)

    Artem'ev, V. A.; Nezvanov, A. Yu.; Nesvizhevsky, V. V.

    2016-01-01

    We discuss properties of the interaction of slow neutrons with nano-dispersed media and their application for neutron reflectors. In order to increase the accuracy of model simulation of the interaction of neutrons with nanopowders, we perform precise quantum mechanical calculation of potential scattering of neutrons on single nanoparticles using the method of phase functions. We compare results of precise calculations with those performed within first Born approximation for nanodiamonds with the radius of 2-5 nm and for neutron energies 3 × 10-7-10-3 eV. Born approximation overestimates the probability of scattering to large angles, while the accuracy of evaluation of integral characteristics (cross sections, albedo) is acceptable. Using Monte-Carlo method, we calculate albedo of neutrons from different layers of piled up diamond nanopowder.

  6. Self-consistent calculation of hyperfine fields and adiabatic potential of impurities in iron

    NASA Astrophysics Data System (ADS)

    Kanamori, Junjiro; Akai, Hisazumi; Akai, Masako

    1984-01-01

    Hyperfine fields of impurities of the atomic number Z=1 56 at the substitutional site and those of light impurities of Z=1 9 at the interstitial sites in ferromagnetic iron are calculated by the KKR method adapted to the system containing a single impurity atom. The potential of the impurity atom is determined self-consistently by use of the local spin density functional formalism. The results for nonmagnetic sp valence impurities agree with those of the previous nonself-consistent calculation by Katayama-Yoshida, Terakura and Kanamori except for a few cases, confirming their theory of the systematic variation of hyperfine fields. The calculation for magnetic impurities of transition elements is presented for the first time in this paper. The calculations mentioned so far assume that impurities are situated at the center of each site. For the purpose of discussing the stability of the impurity positions, the change of the adiabatic potential due to displacements from the center is calculated by carrying out similar self-consistent calculations for off-center impurity positions. It is concluded that positive muon and some light impurities including boron will be displaced from the center when trapped in a vacancy.

  7. S-matrix Calculations of Energy Levels of the Lithium Isoelectronic Sequence

    SciTech Connect

    sapirstein, J; Cheng, K T

    2010-11-02

    A QED approach to the calculation of the spectra of the lithium isoelectronic sequence is implemented. A modified Furry representation based on the Kohn-Sham potential is used to evaluate all one- and two-photon diagrams with the exception of the two-loop Lamb shift. Three-photon diagrams are estimated with Hamiltonian methods. After incorporating recent calculations of the two-loop Lamb shift and recoil corrections a comprehensive tabulation of the 2s, 2p{sub 1/2} and 2p{sub 3/2} energy levels as well as the 2s - 2p{sub 1/2} and 2s - 2p{sub 3/2} transition energies for Z = 10 - 100 is presented.

  8. S-matrix calculations of energy levels of the lithium isoelectronic sequence

    NASA Astrophysics Data System (ADS)

    Sapirstein, J.; Cheng, K. T.

    2012-06-01

    A QED approach to the calculation of the spectra of the lithium isoelectronic sequence is implemented. A modified Furry representation based on the Kohn-Sham potential is used to evaluate all one- and two-photon diagrams with the exception of the two-loop Lamb shift. Three-photon diagrams are estimated with Hamiltonian methods. After incorporating recent calculations of the two-loop Lamb shift and recoil corrections a comprehensive tabulation of the 2s, 2p1/2 and 2p3/2 energy levels as well as the 2s-2p1/2 and 2s-2p3/2 transition energies for Z=10-100 is presented.

  9. S-matrix calculations of energy levels of the lithium isoelectronic sequence

    NASA Astrophysics Data System (ADS)

    Sapirstein, J.; Cheng, K. T.

    2011-01-01

    A QED approach to the calculation of the spectra of the lithium isoelectronic sequence is implemented. A modified Furry representation based on the Kohn-Sham potential is used to evaluate all one- and two-photon diagrams with the exception of the two-loop Lamb shift. Three-photon diagrams are estimated with Hamiltonian methods. After incorporating recent calculations of the two-loop Lamb shift and recoil corrections, a comprehensive tabulation of the 2s, 2p1/2, and 2p3/2 energy levels as well as the 2s-2p1/2 and 2s-2p3/2 transition energies for Z=10-100 is presented.

  10. A consistent calculation of the chemical potential for dense simple fluids.

    PubMed

    Bomont, Jean-Marc

    2006-05-28

    A general method to calculate the excess chemical potential betamuex, that is based on the Kirkwood coupling parameter's dependence of the correlation functions, is presented. The expression for the one particle bridge function B(1)r is derived for simple fluids with spherical interactions. Only the knowledge of the bridge function B(2)r is required. The accuracy of our approach is illustrated for a dense hard sphere fluid. As far as B(2)r is considered as exact, B(1)r is found to be, at high densities, the normalized bridge function -B(2)rB(2)(r=0). This expression ensures a consistent calculation of the excess chemical potential by satisfying implicitly the Gibbs-Duhem constraint. Only the pressure-consistency condition is necessary to calculate the structural and thermodynamic properties of the fluid.

  11. Improved computer programs for calculating potential flow in propulsion system inlets

    NASA Technical Reports Server (NTRS)

    Stockman, N. O.; Farrell, C. A., Jr.

    1977-01-01

    Computer programs to calculate the incompressible potential flow corrected for compressibility in axisymmetric inlets at arbitrary operating conditions are presented. Included are a statement of the problem to be solved, a description of each of the programs and sufficient documentation, including a test case, to enable a user to run the programs.

  12. The Inversion Potential of Ammonia: An Intrinsic Reaction Coordinate Calculation for Student Investigation

    ERIC Educational Resources Information Center

    Halpern, Arthur M.; Ramachandran, B. R.; Glendening, Eric D.

    2007-01-01

    A report is presented to describe how students can be empowered to construct the full, double minimum inversion potential for ammonia by performing intrinsic reaction coordinate calculations. This work can be associated with the third year physical chemistry lecture laboratory or an upper level course in computational chemistry.

  13. A web-based calculator for estimating the profit potential of grain segregation by protein concentration

    Technology Transfer Automated Retrieval System (TEKTRAN)

    By ignoring spatial variability in grain quality, conventional harvesting systems may increase the likelihood that growers will not capture price premiums for high quality grain found within fields. The Grain Segregation Profit Calculator was developed to demonstrate the profit potential of segregat...

  14. Use of Relativistic Effective Core Potentials in the Calculation of Electron-Impact Ionization Cross Sections

    NASA Technical Reports Server (NTRS)

    Huo, Winifred M.; Kim, Yong-Ki

    1999-01-01

    Based on the Binary-Encounter-Bethe (BEB) model, the advantage of using relativistic effective core potentials (RECP) in the calculation of total ionization cross sections of heavy atoms or molecules containing heavy atoms is discussed. Numerical examples for Ar, Kr, Xe, and WF6 are presented.

  15. Computer programs for calculating two-dimensional potential flow through deflected nozzles

    NASA Technical Reports Server (NTRS)

    Hawk, J. D.; Stockman, N. O.

    1979-01-01

    Computer programs to calculate the incompressible potential flow, corrected for compressibility, in two-dimensional nozzles at arbitrary operating conditions are presented. A statement of the problem to be solved, a description of each of the computer programs, and sufficient documentation, including a test case, to enable a user to run the program are included.

  16. Computer programs for calculating two-dimensional potential flow in and about propulsion system inlets

    NASA Technical Reports Server (NTRS)

    Hawk, J. D.; Stockman, N. O.; Farrell, C. A., Jr.

    1978-01-01

    Incompressible potential flow calculations are presented that were corrected for compressibility in two-dimensional inlets at arbitrary operating conditions. Included are a statement of the problem to be solved, a description of each of the computer programs, and sufficient documentation, including a test case, to enable a user to run the program.

  17. Identifying low variance pathways for free energy calculations of molecular transformations in solution phase

    NASA Astrophysics Data System (ADS)

    Pham, Tri T.; Shirts, Michael R.

    2011-07-01

    Improving the efficiency of free energy calculations is important for many biological and materials design applications, such as protein-ligand binding affinities in drug design, partitioning between immiscible liquids, and determining molecular association in soft materials. We show that for any pair potential, moderately accurate estimation of the radial distribution function for a solute molecule is sufficient to accurately estimate the statistical variance of a sampling along a free energy pathway. This allows inexpensive analytical identification of low statistical error free energy pathways. We employ a variety of methods to estimate the radial distribution function (RDF) and find that the computationally cheap two-body "dilute gas" limit performs as well or better than 3D-RISM theory and other approximations for identifying low variance free energy pathways. With a RDF estimate in hand, we can search for pairwise interaction potentials that produce low variance. We give an example of a search minimizing statistical variance of solvation free energy over the entire parameter space of a generalized "soft core" potential. The free energy pathway arising from this optimization procedure has lower curvature in the variance and reduces the total variance by at least 50% compared to the traditional soft core solvation pathway. We also demonstrate that this optimized pathway allows free energies to be estimated with fewer intermediate states due to its low curvature. This free energy variance optimization technique is generalizable to solvation in any homogeneous fluid and for any type of pairwise potential and can be performed in minutes to hours, depending on the method used to estimate g(r).

  18. Caveat Emptor: Calculating All the Costs of Energy.

    ERIC Educational Resources Information Center

    Zinberg, Dorothy S.

    This paper examines the energy problem. Specific topics discussed include the recent history of oil and gas consumption in the United States, conservation, coal, solar energy, and nuclear energy. While solutions to the energy problem differ, there is an urgent need for broad, public debate. Ultimately, the decisions made regarding energy will be…

  19. Correlation energy and dispersion interaction in the ab initio potential energy curve of the neon dimer.

    PubMed

    Bytautas, Laimutis; Ruedenberg, Klaus

    2008-06-01

    A close approximation to the empirical potential energy curve of the neon dimer is obtained by coupled-cluster singles plus doubles plus noniterative triples calculations by using nonaugmented correlation-consistent basis sets without counterpoise corrections and complementing them by three-term extrapolations to the complete basis set limit. The potential energy is resolved into a self-consistent-field Hartree-Fock contribution and a correlation contribution. The latter is shown to decay in the long-range region in accordance with the empirical dispersion expansion.

  20. The calculation of electron chemical potential and ion charge state and their influence on plasma conductivity in electrical explosion of metal wire

    SciTech Connect

    Shi, Zongqian; Wang, Kun; Li, Yao; Shi, Yuanjie; Wu, Jian; Jia, Shenli

    2014-03-15

    The electron chemical potential and ion charge state (average ion charge and ion distribution) are important parameters in calculating plasma conductivity in electrical explosion of metal wire. In this paper, the calculating method of electron chemical potential and ion charge state is discussed at first. For the calculation of electron chemical potential, the ideal free electron gas model and Thomas-Fermi model are compared and analyzed in terms of the coupling constant of plasma. The Thomas-Fermi ionization model, which is used to calculate ion charge state, is compared with the method based on Saha equation. Furthermore, the influence of electron degenerated energy levels and ion excited states in Saha equation on the ion charge state is also analyzed. Then the influence of different calculating methods of electron chemical potential and ion charge state on plasma conductivity is discussed by applying them in the Lee-More conductivity model.

  1. Calculation of transient potential rise on the wind turbine struck by lightning.

    PubMed

    Xiaoqing, Zhang

    2014-01-01

    A circuit model is proposed in this paper for calculating the transient potential rise on the wind turbine struck by lightning. The model integrates the blade, sliding contact site, and tower and grounding system of the wind turbine into an equivalent circuit. The lightning current path from the attachment point to the ground can be fully described by the equivalent circuit. The transient potential responses are obtained in the different positions on the wind turbine by solving the circuit equations. In order to check the validity of the model, the laboratory measurement is made with a reduced-scale wind turbine. The measured potential waveform is compared with the calculated one and a better agreement is shown between them. The practical applicability of the model is also examined by a numerical example of a 2 MW Chinese-built wind turbine. PMID:25254231

  2. Calculation of Transient Potential Rise on the Wind Turbine Struck by Lightning

    PubMed Central

    Xiaoqing, Zhang

    2014-01-01

    A circuit model is proposed in this paper for calculating the transient potential rise on the wind turbine struck by lightning. The model integrates the blade, sliding contact site, and tower and grounding system of the wind turbine into an equivalent circuit. The lightning current path from the attachment point to the ground can be fully described by the equivalent circuit. The transient potential responses are obtained in the different positions on the wind turbine by solving the circuit equations. In order to check the validity of the model, the laboratory measurement is made with a reduced-scale wind turbine. The measured potential waveform is compared with the calculated one and a better agreement is shown between them. The practical applicability of the model is also examined by a numerical example of a 2 MW Chinese-built wind turbine. PMID:25254231

  3. Calculation of transient potential rise on the wind turbine struck by lightning.

    PubMed

    Xiaoqing, Zhang

    2014-01-01

    A circuit model is proposed in this paper for calculating the transient potential rise on the wind turbine struck by lightning. The model integrates the blade, sliding contact site, and tower and grounding system of the wind turbine into an equivalent circuit. The lightning current path from the attachment point to the ground can be fully described by the equivalent circuit. The transient potential responses are obtained in the different positions on the wind turbine by solving the circuit equations. In order to check the validity of the model, the laboratory measurement is made with a reduced-scale wind turbine. The measured potential waveform is compared with the calculated one and a better agreement is shown between them. The practical applicability of the model is also examined by a numerical example of a 2 MW Chinese-built wind turbine.

  4. Calculating solution redox free energies with ab initio quantum mechanical/molecular mechanical minimum free energy path method

    NASA Astrophysics Data System (ADS)

    Zeng, Xiancheng; Hu, Hao; Hu, Xiangqian; Yang, Weitao

    2009-04-01

    A quantum mechanical/molecular mechanical minimum free energy path (QM/MM-MFEP) method was developed to calculate the redox free energies of large systems in solution with greatly enhanced efficiency for conformation sampling. The QM/MM-MFEP method describes the thermodynamics of a system on the potential of mean force surface of the solute degrees of freedom. The molecular dynamics (MD) sampling is only carried out with the QM subsystem fixed. It thus avoids "on-the-fly" QM calculations and thus overcomes the high computational cost in the direct QM/MM MD sampling. In the applications to two metal complexes in aqueous solution, the new QM/MM-MFEP method yielded redox free energies in good agreement with those calculated from the direct QM/MM MD method. Two larger biologically important redox molecules, lumichrome and riboflavin, were further investigated to demonstrate the efficiency of the method. The enhanced efficiency and uncompromised accuracy are especially significant for biochemical systems. The QM/MM-MFEP method thus provides an efficient approach to free energy simulation of complex electron transfer reactions.

  5. Calculating solution redox free energies with ab initio quantum mechanical/molecular mechanical minimum free energy path method

    SciTech Connect

    Zeng Xiancheng; Hu Hao; Hu Xiangqian; Yang Weitao

    2009-04-28

    A quantum mechanical/molecular mechanical minimum free energy path (QM/MM-MFEP) method was developed to calculate the redox free energies of large systems in solution with greatly enhanced efficiency for conformation sampling. The QM/MM-MFEP method describes the thermodynamics of a system on the potential of mean force surface of the solute degrees of freedom. The molecular dynamics (MD) sampling is only carried out with the QM subsystem fixed. It thus avoids 'on-the-fly' QM calculations and thus overcomes the high computational cost in the direct QM/MM MD sampling. In the applications to two metal complexes in aqueous solution, the new QM/MM-MFEP method yielded redox free energies in good agreement with those calculated from the direct QM/MM MD method. Two larger biologically important redox molecules, lumichrome and riboflavin, were further investigated to demonstrate the efficiency of the method. The enhanced efficiency and uncompromised accuracy are especially significant for biochemical systems. The QM/MM-MFEP method thus provides an efficient approach to free energy simulation of complex electron transfer reactions.

  6. California's biomass and its energy potential

    SciTech Connect

    Lucarelli, F.B. Jr.

    1980-04-01

    The potentials for using California's biomass for energy have been assessed. The study relies on the recent work of Amory Lovins and Lawrence Berkeley Laboratory's (LBL) Distributed Energy System's Project to specify an energy future for Californians. These works identify transportation fuels as the most valuable energy conversion for biomass. Within this context, the extent of five categories of terrestial biomass is estimated, in addition to the environmental impacts and monetary cost of collecting and transporting each biomass category. Estimates of the costs of transforming biomass into different fuels as well as a survey of government's role in a biomass energy program are presented. The major findings are summarized below. (1) California's existing biomass resources are sufficient to provide only 20 percent of its future liquid fuel requirements. (2) Meeting the full transportation demand with biomass derived fuels will require the development of exotic biomass sources such as kelp farms and significant reductions in automobile travel in the State. (3) Under assumptions of moderate increases in gasoline prices and without major new government incentives, the cost of transforming biomass into transport fuels will be competitive with the price of gasoline on a Btu basis by the year 1990. (4) The environmental impacts of collecting most forms of biomass are beneficial and should reduce air pollution from agricultural burning and water pollution from feedlot and dairy farm runoff. Moreover, the collection of logging residues should improve timber stand productivity and the harvest of chaparral should reduce the risk of wildfire in the State. (5) The institutional context for implementing biomass energy projects is complex and fragmented.

  7. Computed potential energy surfaces for chemical reactions

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.; Levin, Eugene

    1993-01-01

    A new global potential energy surface (PES) is being generated for O(P-3) + H2 yields OH + H. This surface is being fit using the rotated Morse oscillator method, which was used to fit the previous POL-CI surface. The new surface is expected to be more accurate and also includes a much more complete sampling of bent geometries. A new study has been undertaken of the reaction N + O2 yields NO + O. The new studies have focused on the region of the surface near a possible minimum corresponding to the peroxy form of NOO. A large portion of the PES for this second reaction has been mapped out. Since state to state cross sections for the reaction are important in the chemistry of high temperature air, these studies will probably be extended to permit generation of a new global potential for reaction.

  8. Accurate and Efficient Calculation of van der Waals Interactions Within Density Functional Theory by Local Atomic Potential Approach

    SciTech Connect

    Sun, Y. Y.; Kim, Y. H.; Lee, K.; Zhang, S. B.

    2008-01-01

    Density functional theory (DFT) in the commonly used local density or generalized gradient approximation fails to describe van der Waals (vdW) interactions that are vital to organic, biological, and other molecular systems. Here, we propose a simple, efficient, yet accurate local atomic potential (LAP) approach, named DFT+LAP, for including vdW interactions in the framework of DFT. The LAPs for H, C, N, and O are generated by fitting the DFT+LAP potential energy curves of small molecule dimers to those obtained from coupled cluster calculations with single, double, and perturbatively treated triple excitations, CCSD(T). Excellent transferability of the LAPs is demonstrated by remarkable agreement with the JSCH-2005 benchmark database [P. Jurecka et al. Phys. Chem. Chem. Phys. 8, 1985 (2006)], which provides the interaction energies of CCSD(T) quality for 165 vdW and hydrogen-bonded complexes. For over 100 vdW dominant complexes in this database, our DFT+LAP calculations give a mean absolute deviation from the benchmark results less than 0.5 kcal/mol. The DFT+LAP approach involves no extra computational cost other than standard DFT calculations and no modification of existing DFT codes, which enables straightforward quantum simulations, such as ab initio molecular dynamics, on biomolecular systems, as well as on other organic systems.

  9. The potential, limitations, and challenges of divide and conquer quantum electronic structure calculations on energetic materials.

    SciTech Connect

    Tucker, Jon R.; Magyar, Rudolph J.

    2012-02-01

    High explosives are an important class of energetic materials used in many weapons applications. Even with modern computers, the simulation of the dynamic chemical reactions and energy release is exceedingly challenging. While the scale of the detonation process may be macroscopic, the dynamic bond breaking responsible for the explosive release of energy is fundamentally quantum mechanical. Thus, any method that does not adequately describe bonding is destined to lack predictive capability on some level. Performing quantum mechanics calculations on systems with more than dozens of atoms is a gargantuan task, and severe approximation schemes must be employed in practical calculations. We have developed and tested a divide and conquer (DnC) scheme to obtain total energies, forces, and harmonic frequencies within semi-empirical quantum mechanics. The method is intended as an approximate but faster solution to the full problem and is possible due to the sparsity of the density matrix in many applications. The resulting total energy calculation scales linearly as the number of subsystems, and the method provides a path-forward to quantum mechanical simulations of millions of atoms.

  10. Spectroscopic constants and potential energy curves of yttrium carbide (YC).

    PubMed

    Suo, Bingbing; Balasubramanian, Krishnan

    2007-06-14

    The potential energy curves of the low-lying electronic states of yttrium carbide (YC) and its cation are calculated at the complete active space self-consistent field and the multireference single and double excitation configuration interaction (MRSDCI) levels of theory. Fifteen low-lying electronic states of YC with different spin and spatial symmetries were identified. The X (4)Sigma- state prevails as the ground state of YC, and a low-lying excited A (4)Pi state is found to be 1661 cm(-1) higher at the MRSDCI level. The computations of the authors support the assignment of the observed spectra to a B (4)Delta(Omega=72)<--A (4)Pi(Omega=52) transition with a reinterpretation that the A (4)Pi state is appreciably populated under the experimental conditions as it is less than 2000 cm(-1) of the X (4)Sigma- ground state, and the previously suggested (4)Pi ground state is reassigned to the first low-lying excited state of YC. The potential energy curves of YC+ confirm a previous prediction by Seivers et al. [J. Chem. Phys. 105, 6322 (1996)] that the ground state of YC+ is formed through a second pathway at higher energies. The calculated ionization energy of YC is 6.00 eV, while the adiabatic electron affinity is 0.95 eV at the MRSDCI level. The computed ionization energy of YC and dissociation energy of YC+ confirm the revised experimental estimates provided by Seivers et al. although direct experimental measurements yielded results with greater errors due to uncertainty in collisional cross sections for YC+ formation.

  11. Spectroscopic constants and potential energy curves of yttrium carbide (YC)

    NASA Astrophysics Data System (ADS)

    Suo, Bingbing; Balasubramanian, Krishnan

    2007-06-01

    The potential energy curves of the low-lying electronic states of yttrium carbide (YC) and its cation are calculated at the complete active space self-consistent field and the multireference single and double excitation configuration interaction (MRSDCI) levels of theory. Fifteen low-lying electronic states of YC with different spin and spatial symmetries were identified. The XΣ-4 state prevails as the ground state of YC, and a low-lying excited AΠ4 state is found to be 1661cm-1 higher at the MRSDCI level. The computations of the authors support the assignment of the observed spectra to a BΔ4(Ω =7/2)←AΠ4(Ω=5/2) transition with a reinterpretation that the AΠ4 state is appreciably populated under the experimental conditions as it is less than 2000cm-1 of the XΣ-4 ground state, and the previously suggested Π4 ground state is reassigned to the first low-lying excited state of YC. The potential energy curves of YC + confirm a previous prediction by Seivers et al. [J. Chem. Phys. 105, 6322 (1996)] that the ground state of YC+ is formed through a second pathway at higher energies. The calculated ionization energy of YC is 6.00eV, while the adiabatic electron affinity is 0.95eV at the MRSDCI level. The computed ionization energy of YC and dissociation energy of YC+ confirm the revised experimental estimates provided by Seivers et al. although direct experimental measurements yielded results with greater errors due to uncertainty in collisional cross sections for YC+ formation.

  12. Intermolecular potential energy surface and thermophysical properties of ethylene oxide

    SciTech Connect

    Crusius, Johann-Philipp Hassel, Egon; Hellmann, Robert; Bich, Eckard

    2014-10-28

    A six-dimensional potential energy hypersurface (PES) for two interacting rigid ethylene oxide (C{sub 2}H{sub 4}O) molecules was determined from high-level quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the MP2 and CCSD(T) levels of theory was utilized to determine interaction energies for 10178 configurations of two molecules. An analytical site-site potential function with 19 sites per ethylene oxide molecule was fitted to the interaction energies and fine tuned to agree with data for the second acoustic virial coefficient from accurate speed of sound measurements. The PES was validated by computing the second virial coefficient, shear viscosity, and thermal conductivity. The values of these properties are substantiated by the best experimental data as they tend to fall within the uncertainty intervals and also obey the experimental temperature functions, except for viscosity, where experimental data are insufficient. Due to the lack of reliable data, especially for the transport properties, our calculated values are currently the most accurate estimates for these properties of ethylene oxide.

  13. Towards a spectroscopically accurate set of potentials for heavy hydride laser cooling candidates: Effective core potential calculations of BaH

    NASA Astrophysics Data System (ADS)

    Moore, Keith; McLaughlin, Brendan M.; Lane, Ian C.

    2016-04-01

    BaH (and its isotopomers) is an attractive molecular candidate for laser cooling to ultracold temperatures and a potential precursor for the production of ultracold gases of hydrogen and deuterium. The theoretical challenge is to simulate the laser cooling cycle as reliably as possible and this paper addresses the generation of a highly accurate ab initio 2Σ+ potential for such studies. The performance of various basis sets within the multi-reference configuration-interaction (MRCI) approximation with the Davidson correction is tested and taken to the Complete Basis Set (CBS) limit. It is shown that the calculated molecular constants using a 46 electron effective core-potential and even-tempered augmented polarized core-valence basis sets (aug-pCVnZ-PP, n = 4 and 5) but only including three active electrons in the MRCI calculation are in excellent agreement with the available experimental values. The predicted dissociation energy De for the X2Σ+ state (extrapolated to the CBS limit) is 16 895.12 cm-1 (2.094 eV), which agrees within 0.1% of a revised experimental value of <16 910.6 cm-1, while the calculated re is within 0.03 pm of the experimental result.

  14. Calculation procedures for potential and viscous flow solutions for engine inlets

    NASA Technical Reports Server (NTRS)

    Albers, J. A.; Stockman, N. O.

    1973-01-01

    The method and basic elements of computer solutions for both potential flow and viscous flow calculations for engine inlets are described. The procedure is applicable to subsonic conventional (CTOL), short-haul (STOL), and vertical takeoff (VTOL) aircraft engine nacelles operating in a compressible viscous flow. The calculated results compare well with measured surface pressure distributions for a number of model inlets. The paper discusses the uses of the program in both the design and analysis of engine inlets, with several examples given for VTOL lift fans, acoustic splitters, and for STOL engine nacelles. Several test support applications are also given.

  15. Complex-scaling of screened Coulomb potentials for resonance calculations utilizing the modified Bessel functions

    NASA Astrophysics Data System (ADS)

    Jiao, Li-Guang; Ho, Yew Kam

    2014-05-01

    The screened Coulomb potential (SCP) has been extensively used in atomic physics, nuclear physics, quantum chemistry and plasma physics. However, an accurate calculation for atomic resonances under SCP is still a challenging task for various methods. Within the complex-scaling computational scheme, we have developed a method utilizing the modified Bessel functions to calculate doubly-excited resonances in two-electron atomic systems with configuration interaction-type basis. To test the validity of our method, we have calculated S- and P-wave resonance states of the helium atom with various screening strengths, and have found good agreement with earlier calculations using different methods. Our present method can be applied to calculate high-lying resonances associated with high excitation thresholds of the He+ ion, and with high-angular-momentum states. The derivation and calculation details of our present investigation together with new results of high-angular-momentum states will be presented at the meeting. Supported by NSC of Taiwan.

  16. On the importance of full-dimensionality in low-energy molecular scattering calculations.

    PubMed

    Faure, Alexandre; Jankowski, Piotr; Stoecklin, Thierry; Szalewicz, Krzysztof

    2016-01-01

    Scattering of H2 on CO is of great importance in astrophysics and also is a benchmark system for comparing theory to experiment. We present here a new 6-dimensional potential energy surface for the ground electronic state of H2-CO with an estimated uncertainty of about 0.6 cm(-1) in the global minimum region, several times smaller than achieved earlier. This potential has been used in nearly exact 6-dimensional quantum scattering calculations to compute state-to-state cross-sections measured in low-energy crossed-beam experiments. Excellent agreement between theory and experiment has been achieved in all cases. We also show that the fully 6-dimensional approach is not needed with the current accuracy of experimental data since an equally good agreement with experiment was obtained using only a 4-dimensional treatment, which validates the rigid-rotor approach widely used in scattering calculations. This finding, which disagrees with some literature statements, is important since for larger systems full-dimensional scattering calculations are currently not possible. PMID:27333870

  17. On the importance of full-dimensionality in low-energy molecular scattering calculations

    PubMed Central

    Faure, Alexandre; Jankowski, Piotr; Stoecklin, Thierry; Szalewicz, Krzysztof

    2016-01-01

    Scattering of H2 on CO is of great importance in astrophysics and also is a benchmark system for comparing theory to experiment. We present here a new 6-dimensional potential energy surface for the ground electronic state of H2-CO with an estimated uncertainty of about 0.6 cm−1 in the global minimum region, several times smaller than achieved earlier. This potential has been used in nearly exact 6-dimensional quantum scattering calculations to compute state-to-state cross-sections measured in low-energy crossed-beam experiments. Excellent agreement between theory and experiment has been achieved in all cases. We also show that the fully 6-dimensional approach is not needed with the current accuracy of experimental data since an equally good agreement with experiment was obtained using only a 4-dimensional treatment, which validates the rigid-rotor approach widely used in scattering calculations. This finding, which disagrees with some literature statements, is important since for larger systems full-dimensional scattering calculations are currently not possible. PMID:27333870

  18. On the calculation of the absolute grand potential of confined smectic-A phases

    NASA Astrophysics Data System (ADS)

    Huang, Chien-Cheng; Baus, Marc; Ryckaert, Jean-Paul

    2015-09-01

    We determine the absolute grand potential Λ along a confined smectic-A branch of a calamitic liquid crystal system enclosed in a slit pore of transverse area A and width L, using the rod-rod Gay-Berne potential and a rod-wall potential favouring perpendicular orientation at the walls. For a confined phase with an integer number of smectic layers sandwiched between the opposite walls, we obtain the excess properties (excess grand potential Λexc, solvation force fs and adsorption Γ) with respect to the bulk phase at the same μ (chemical potential) and T (temperature) state point. While usual thermodynamic integration methods are used along the confined smectic branch to estimate the grand potential difference as μ is varied at fixed L, T, the absolute grand potential at one reference state point is obtained via the evaluation of the absolute Helmholtz free energy in the (N, L, A, T) canonical ensemble. It proceeds via a sequence of free energy difference estimations involving successively the cost of localising rods on layers and the switching on of a one-dimensional harmonic field to keep layers integrity coupled to the elimination of inter-layers and wall interactions. The absolute free energy of the resulting set of fully independent layers of interacting rods is finally estimated via the existing procedures. This work opens the way to the computer simulation study of phase transitions implying confined layered phases.

  19. Recent advances in QM/MM free energy calculations using reference potentials☆

    PubMed Central

    Duarte, Fernanda; Amrein, Beat A.; Blaha-Nelson, David; Kamerlin, Shina C.L.

    2015-01-01

    Background Recent years have seen enormous progress in the development of methods for modeling (bio)molecular systems. This has allowed for the simulation of ever larger and more complex systems. However, as such complexity increases, the requirements needed for these models to be accurate and physically meaningful become more and more difficult to fulfill. The use of simplified models to describe complex biological systems has long been shown to be an effective way to overcome some of the limitations associated with this computational cost in a rational way. Scope of review Hybrid QM/MM approaches have rapidly become one of the most popular computational tools for studying chemical reactivity in biomolecular systems. However, the high cost involved in performing high-level QM calculations has limited the applicability of these approaches when calculating free energies of chemical processes. In this review, we present some of the advances in using reference potentials and mean field approximations to accelerate high-level QM/MM calculations. We present illustrative applications of these approaches and discuss challenges and future perspectives for the field. Major conclusions The use of physically-based simplifications has shown to effectively reduce the cost of high-level QM/MM calculations. In particular, lower-level reference potentials enable one to reduce the cost of expensive free energy calculations, thus expanding the scope of problems that can be addressed. General significance As was already demonstrated 40 years ago, the usage of simplified models still allows one to obtain cutting edge results with substantially reduced computational cost. This article is part of a Special Issue entitled Recent developments of molecular dynamics. PMID:25038480

  20. Potential energy surfaces of superheavy nuclei

    SciTech Connect

    Bender, M.; Rutz, K.; Maruhn, J.A.; Greiner, W.; Reinhard, P.-G. Rutz, K.; Maruhn, J.A.; Greiner, W.

    1998-10-01

    We investigate the structure of the potential energy surfaces of the superheavy nuclei {sub 158}{sup 258}Fm{sub 100}, {sub 156}{sup 264}Hs{sub 108}, {sub 166}{sup 278}112, {sub 184}{sup 298}114, and {sub 172}{sup 292}120 within the framework of self-consistent nuclear models, i.e., the Skyrme-Hartree-Fock approach and the relativistic mean-field model. We compare results obtained with one representative parametrization of each model which is successful in describing superheavy nuclei. We find systematic changes as compared to the potential energy surfaces of heavy nuclei in the uranium region: there is no sufficiently stable fission isomer any more, the importance of triaxial configurations to lower the first barrier fades away, and asymmetric fission paths compete down to rather small deformation. Comparing the two models, it turns out that the relativistic mean-field model gives generally smaller fission barriers. {copyright} {ital 1998} {ital The American Physical Society}

  1. The Direct Calculation of Solid and Liquid Free Energies of Metals and Alloys Using the Embedded Atom Method

    NASA Astrophysics Data System (ADS)

    Song, Xueyu; Morris, James

    2003-03-01

    We present a method of directly and accurately calculating the free energy of metals and alloys, directly from models such as the Embedded Atom Method (EAM). An effective pair potential is defined, and used in an extended Weeks-Chandler-Andersen (WCA) approach. An effective hard-sphere density is defined, and perturbations from the hard-sphere limit are calculated using the pair correlation functions calculated from density functional theory. Calculations using the Mei and Davenport EAM potential for Al, with the modifications of Sturgeon and Laird, demonstrate the accuracy of the approach for both the liquid and solid phases by comparison with simulations. These results are the first step toward the direct calculation of the solid-liquid interfacial free energy for metallic systems, an important parameter for classical nucleation theory and for solidification dynamics. Our recent simulation results for the interfacial free energy provides an important test of the inhomogeneous theory. We also present preliminary results for binary systems, where the direct calculation of phase diagrams based upon the inter-atomic potentials will be compared with simulations. The approach will also allow for the direct calculation of the properties of under-cooled liquid metals and alloys.

  2. CALCULATION OF GAMMA SPECTRA IN A PLASTIC SCINTILLATOR FOR ENERGY CALIBRATIONAND DOSE COMPUTATION.

    PubMed

    Kim, Chankyu; Yoo, Hyunjun; Kim, Yewon; Moon, Myungkook; Kim, Jong Yul; Kang, Dong Uk; Lee, Daehee; Kim, Myung Soo; Cho, Minsik; Lee, Eunjoong; Cho, Gyuseong

    2016-09-01

    Plastic scintillation detectors have practical advantages in the field of dosimetry. Energy calibration of measured gamma spectra is important for dose computation, but it is not simple in the plastic scintillators because of their different characteristics and a finite resolution. In this study, the gamma spectra in a polystyrene scintillator were calculated for the energy calibration and dose computation. Based on the relationship between the energy resolution and estimated energy broadening effect in the calculated spectra, the gamma spectra were simply calculated without many iterations. The calculated spectra were in agreement with the calculation by an existing method and measurements. PMID:27127208

  3. Evaluation of global onshore wind energy potential and generation costs.

    PubMed

    Zhou, Yuyu; Luckow, Patrick; Smith, Steven J; Clarke, Leon

    2012-07-17

    In this study, we develop an updated global estimate of onshore wind energy potential using reanalysis wind speed data, along with updated wind turbine technology performance, land suitability factors, cost assumptions, and explicit consideration of transmission distance in the calculation of transmission costs. We find that wind has the potential to supply a significant portion of the world energy needs, although this potential varies substantially by region and with assumptions such as on what types of land can be used to site wind farms. Total global economic wind potential under central assumptions, that is, intermediate between optimistic and pessimistic, is estimated to be approximately 119.5 petawatt hours per year (13.6 TW) at less than 9 cents/kWh. A sensitivity analysis of eight key parameters is presented. Wind potential is sensitive to a number of input parameters, particularly wind speed (varying by -70% to +450% at less than 9 cents/kWh), land suitability (by -55% to +25%), turbine density (by -60% to +80%), and cost and financing options (by -20% to +200%), many of which have important policy implications. As a result of sensitivities studied here we suggest that further research intended to inform wind supply curve development focus not purely on physical science, such as better resolved wind maps, but also on these less well-defined factors, such as land-suitability, that will also have an impact on the long-term role of wind power.

  4. Evaluation of global onshore wind energy potential and generation costs.

    PubMed

    Zhou, Yuyu; Luckow, Patrick; Smith, Steven J; Clarke, Leon

    2012-07-17

    In this study, we develop an updated global estimate of onshore wind energy potential using reanalysis wind speed data, along with updated wind turbine technology performance, land suitability factors, cost assumptions, and explicit consideration of transmission distance in the calculation of transmission costs. We find that wind has the potential to supply a significant portion of the world energy needs, although this potential varies substantially by region and with assumptions such as on what types of land can be used to site wind farms. Total global economic wind potential under central assumptions, that is, intermediate between optimistic and pessimistic, is estimated to be approximately 119.5 petawatt hours per year (13.6 TW) at less than 9 cents/kWh. A sensitivity analysis of eight key parameters is presented. Wind potential is sensitive to a number of input parameters, particularly wind speed (varying by -70% to +450% at less than 9 cents/kWh), land suitability (by -55% to +25%), turbine density (by -60% to +80%), and cost and financing options (by -20% to +200%), many of which have important policy implications. As a result of sensitivities studied here we suggest that further research intended to inform wind supply curve development focus not purely on physical science, such as better resolved wind maps, but also on these less well-defined factors, such as land-suitability, that will also have an impact on the long-term role of wind power. PMID:22715929

  5. The Role of Molecular Dynamics Potential of Mean Force Calculations in the Investigation of Enzyme Catalysis.

    PubMed

    Yang, Y; Pan, L; Lightstone, F C; Merz, K M

    2016-01-01

    The potential of mean force simulations, widely applied in Monte Carlo or molecular dynamics simulations, are useful tools to examine the free energy variation as a function of one or more specific reaction coordinate(s) for a given system. Implementation of the potential of mean force in the simulations of biological processes, such as enzyme catalysis, can help overcome the difficulties of sampling specific regions on the energy landscape and provide useful insights to understand the catalytic mechanism. The potential of mean force simulations usually require many, possibly parallelizable, short simulations instead of a few extremely long simulations and, therefore, are fairly manageable for most research facilities. In this chapter, we provide detailed protocols for applying the potential of mean force simulations to investigate enzymatic mechanisms for several different enzyme systems. PMID:27498632

  6. Energy potential of sugarcane and sweet sorghum

    SciTech Connect

    Elawad, S.H.; Gascho, G.J.; Shih, S.F.

    1980-01-01

    The potential of sugarcane and sweet sorghum as raw materials for the production of ethanol and petrochemical substitutes is discussed. Both crops belong to the grass family and are classified as C/sub 4/ malateformers which have the highest rate of photosynthesis among terrestrial plants. Large amounts of biomass are required to supply a significant fraction of US energy consumption. Biomass production could be substantially increased by including tops and leaves, adopting narrow row spacing and improving cultural practices. This presents challenges for cultivating, harvesting, and hauling the biomass to processing centers. Large plants and heavy capital investment are essential for energy production. Ethanol and ammonia are the most promising candidates of a biomass program. If sugarcane were to be used for biomass production, breeding programs should be directed for more fermentable sugars and fiber. Energy research on sweet sorghum should be done with syrup varieties. Sweet sorghum needs to be incorporated with other crops because of its short growing season. The disposal of stillage from an extensive ethanol industry may pose environmental problems.

  7. Shear-deformation-potential constant of the conduction-band minima of Si: Pseudopotential calculations

    NASA Astrophysics Data System (ADS)

    Li, Ming-Fu; Gu, Zong-Quan; Wang, Jian-Qing

    1990-09-01

    We have calculated the value of the shear-deformation-potential constant Ξu of the conduction-band minima of Si and its temperature coefficient dΞu/dT. The value of Ξu is 9.0 eV for an ab initio pseudopotential calculation and 10.8 eV by the empirical-pseudopotential method (EPM), in good agreement with our experiment. The EPM calculations of the temperature dependence of Ξu yield the values of (dΞu/dT)||DW=-0.04 meV/K due to the Debye-Waller contribution, and (dΞu/dT)||TE=-0.04 meV/K for thermal expansion. We suspect and suggest that the existing experimental value of dΞu/dT~=+3 meV/K is unreliable due to large experimental uncertainty.

  8. Calculation of positron binding energies using the generalized any particle propagator theory

    SciTech Connect

    Romero, Jonathan; Charry, Jorge A.; Flores-Moreno, Roberto; Varella, Márcio T. do N.; Reyes, Andrés

    2014-09-21

    We recently extended the electron propagator theory to any type of quantum species based in the framework of the Any-Particle Molecular Orbital (APMO) approach [J. Romero, E. Posada, R. Flores-Moreno, and A. Reyes, J. Chem. Phys. 137, 074105 (2012)]. The generalized any particle molecular orbital propagator theory (APMO/PT) was implemented in its quasiparticle second order version in the LOWDIN code and was applied to calculate nuclear quantum effects in electron binding energies and proton binding energies in molecular systems [M. Díaz-Tinoco, J. Romero, J. V. Ortiz, A. Reyes, and R. Flores-Moreno, J. Chem. Phys. 138, 194108 (2013)]. In this work, we present the derivation of third order quasiparticle APMO/PT methods and we apply them to calculate positron binding energies (PBEs) of atoms and molecules. We calculated the PBEs of anions and some diatomic molecules using the second order, third order, and renormalized third order quasiparticle APMO/PT approaches and compared our results with those previously calculated employing configuration interaction (CI), explicitly correlated and quantum Montecarlo methodologies. We found that renormalized APMO/PT methods can achieve accuracies of ∼0.35 eV for anionic systems, compared to Full-CI results, and provide a quantitative description of positron binding to anionic and highly polar species. Third order APMO/PT approaches display considerable potential to study positron binding to large molecules because of the fifth power scaling with respect to the number of basis sets. In this regard, we present additional PBE calculations of some small polar organic molecules, amino acids and DNA nucleobases. We complement our numerical assessment with formal and numerical analyses of the treatment of electron-positron correlation within the quasiparticle propagator approach.

  9. Calculation of positron binding energies using the generalized any particle propagator theory.

    PubMed

    Romero, Jonathan; Charry, Jorge A; Flores-Moreno, Roberto; Varella, Márcio T do N; Reyes, Andrés

    2014-09-21

    We recently extended the electron propagator theory to any type of quantum species based in the framework of the Any-Particle Molecular Orbital (APMO) approach [J. Romero, E. Posada, R. Flores-Moreno, and A. Reyes, J. Chem. Phys. 137, 074105 (2012)]. The generalized any particle molecular orbital propagator theory (APMO/PT) was implemented in its quasiparticle second order version in the LOWDIN code and was applied to calculate nuclear quantum effects in electron binding energies and proton binding energies in molecular systems [M. Díaz-Tinoco, J. Romero, J. V. Ortiz, A. Reyes, and R. Flores-Moreno, J. Chem. Phys. 138, 194108 (2013)]. In this work, we present the derivation of third order quasiparticle APMO/PT methods and we apply them to calculate positron binding energies (PBEs) of atoms and molecules. We calculated the PBEs of anions and some diatomic molecules using the second order, third order, and renormalized third order quasiparticle APMO/PT approaches and compared our results with those previously calculated employing configuration interaction (CI), explicitly correlated and quantum Montecarlo methodologies. We found that renormalized APMO/PT methods can achieve accuracies of ~0.35 eV for anionic systems, compared to Full-CI results, and provide a quantitative description of positron binding to anionic and highly polar species. Third order APMO/PT approaches display considerable potential to study positron binding to large molecules because of the fifth power scaling with respect to the number of basis sets. In this regard, we present additional PBE calculations of some small polar organic molecules, amino acids and DNA nucleobases. We complement our numerical assessment with formal and numerical analyses of the treatment of electron-positron correlation within the quasiparticle propagator approach.

  10. Calculation of positron binding energies using the generalized any particle propagator theory

    NASA Astrophysics Data System (ADS)

    Romero, Jonathan; Charry, Jorge A.; Flores-Moreno, Roberto; Varella, Márcio T. do N.; Reyes, Andrés

    2014-09-01

    We recently extended the electron propagator theory to any type of quantum species based in the framework of the Any-Particle Molecular Orbital (APMO) approach [J. Romero, E. Posada, R. Flores-Moreno, and A. Reyes, J. Chem. Phys. 137, 074105 (2012)]. The generalized any particle molecular orbital propagator theory (APMO/PT) was implemented in its quasiparticle second order version in the LOWDIN code and was applied to calculate nuclear quantum effects in electron binding energies and proton binding energies in molecular systems [M. Díaz-Tinoco, J. Romero, J. V. Ortiz, A. Reyes, and R. Flores-Moreno, J. Chem. Phys. 138, 194108 (2013)]. In this work, we present the derivation of third order quasiparticle APMO/PT methods and we apply them to calculate positron binding energies (PBEs) of atoms and molecules. We calculated the PBEs of anions and some diatomic molecules using the second order, third order, and renormalized third order quasiparticle APMO/PT approaches and compared our results with those previously calculated employing configuration interaction (CI), explicitly correlated and quantum Montecarlo methodologies. We found that renormalized APMO/PT methods can achieve accuracies of ˜0.35 eV for anionic systems, compared to Full-CI results, and provide a quantitative description of positron binding to anionic and highly polar species. Third order APMO/PT approaches display considerable potential to study positron binding to large molecules because of the fifth power scaling with respect to the number of basis sets. In this regard, we present additional PBE calculations of some small polar organic molecules, amino acids and DNA nucleobases. We complement our numerical assessment with formal and numerical analyses of the treatment of electron-positron correlation within the quasiparticle propagator approach.

  11. Moire pattern interlayer potentials in van der Waals materials from high level ab initio calculations

    NASA Astrophysics Data System (ADS)

    Jung, Jeil; Leconte, Nicolas; Lebegue, Sebastien; Gould, Timothy

    Stacking-dependent interlayer interactions are important for understanding the structural and electronic properties in incommensurable two dimensional material assemblies where long-range moiré patterns arise due to small lattice constant mismatch or twist angles. We study the stacking-dependent interlayer coupling energies between graphene (G) and hexagonal boron nitride (BN) single layers for different possible combinations such as G/G, G/BN and BN/BN using high-level EXX+RPA ab initio calculations. The total energies differ substantially when compared with conventional LDA, but for stacking-dependent total energy differences we find that the dominance of short-range covalent-type binding over the longer-ranged van der Waals tails near equilibrium geometries renders the LDA as a reasonable starting point for ab initio calculation based analyses for the systems we have studied. Our calculations are useful input for study of strains originated by interlayer interactions in incommensurable 2D van der Waals crystals.

  12. Chemisorbed-molecule potential energy surfaces and DIET processes

    NASA Astrophysics Data System (ADS)

    Jennison, D. R.; Stechel, E. B.; Burns, A. R.; Li, Y. S.

    1995-06-01

    We report the use of the local-density approximation, with and without gradient corrections, for the calculation of ground-state potential energy surfaces (PESs) for chemisorbed molecules. We focus on chemisorbed NO and ammonia on Pd(1 1 1) and compare our results with the latest experimental information. We then turn to two aspects of excited-state PESs. First, we compare first-principles calculations of the forces on an ammonia ion as a function of distance from the surface. We find that the image-charge model fails significantly at distances which are the most relevant for dynamics, closer than ˜3 Å, and discuss reasons for the failure. We then summarize a purely electronic adiabatic model of the moleuule-surface bond and use empirical parameters to estimate hot carrier-produced excited states of chemisorbed NO. We find multiple PESs and a novel interpretation of the π ∗ resonance, seen in inverse photoemission.

  13. Microscopic calculation of {alpha}-decay half-lives with a deformed potential

    SciTech Connect

    Ni Dongdong; Ren Zhongzhou

    2009-11-15

    A new version of the generalized density-dependent cluster model is presented to describe an {alpha} particle tunneling through a deformed potential barrier. The microscopic deformed potential is numerically constructed in the double-folding model by the multipole expansion method. The decay width is computed using the coupled-channel Schroedinger equation with outgoing wave boundary conditions. We perform a systematic calculation on {alpha}-decay half-lives of even-even nuclei ranging from Z=52 to Z=104, including 65 well-deformed ones. The calculated {alpha}-decay half-lives are found to be in good agreement with the experimental values. There also exists good agreement with the available experimental branching ratios for well-deformed systems.

  14. Calculation of high-order virial coefficients for the square-well potential

    NASA Astrophysics Data System (ADS)

    Do, Hainam; Feng, Chao; Schultz, Andrew J.; Kofke, David A.; Wheatley, Richard J.

    2016-07-01

    Accurate virial coefficients BN(λ ,ɛ ) (where ɛ is the well depth) for the three-dimensional square-well and square-step potentials are calculated for orders N = 5 - 9 and well widths λ =1.1 -2.0 using a very fast recursive method. The efficiency of the algorithm is enhanced significantly by exploiting permutation symmetry and by storing integrands for reuse during the calculation. For N = 9 the storage requirements become sufficiently large that a parallel algorithm is developed. The methodology is general and is applicable to other discrete potentials. The computed coefficients are precise even near the critical temperature, and thus open up possibilities for analysis of criticality of the system, which is currently not accessible by any other means.

  15. Calculation of high-order virial coefficients for the square-well potential.

    PubMed

    Do, Hainam; Feng, Chao; Schultz, Andrew J; Kofke, David A; Wheatley, Richard J

    2016-07-01

    Accurate virial coefficients B_{N}(λ,ɛ) (where ɛ is the well depth) for the three-dimensional square-well and square-step potentials are calculated for orders N=5-9 and well widths λ=1.1-2.0 using a very fast recursive method. The efficiency of the algorithm is enhanced significantly by exploiting permutation symmetry and by storing integrands for reuse during the calculation. For N=9 the storage requirements become sufficiently large that a parallel algorithm is developed. The methodology is general and is applicable to other discrete potentials. The computed coefficients are precise even near the critical temperature, and thus open up possibilities for analysis of criticality of the system, which is currently not accessible by any other means. PMID:27575230

  16. Multireference configuration interaction calculations of the first six ionization potentials of the uranium atom

    NASA Astrophysics Data System (ADS)

    Bross, David H.; Parmar, Payal; Peterson, Kirk A.

    2015-11-01

    The first 6 ionization potentials (IPs) of the uranium atom have been calculated using multireference configuration interaction (MRCI+Q) with extrapolations to the complete basis set limit using new all-electron correlation consistent basis sets. The latter was carried out with the third-order Douglas-Kroll-Hess Hamiltonian. Correlation down through the 5s5p5d electrons has been taken into account, as well as contributions to the IPs due to the Lamb shift. Spin-orbit coupling contributions calculated at the 4-component Kramers restricted configuration interaction level, as well as the Gaunt term computed at the Dirac-Hartree-Fock level, were added to the best scalar relativistic results. The final ionization potentials are expected to be accurate to at least 5 kcal/mol (0.2 eV) and thus more reliable than the current experimental values of IP3 through IP6.

  17. Multireference configuration interaction calculations of the first six ionization potentials of the uranium atom

    SciTech Connect

    Bross, David H.; Parmar, Payal; Peterson, Kirk A.

    2015-11-14

    The first 6 ionization potentials (IPs) of the uranium atom have been calculated using multireference configuration interaction (MRCI+Q) with extrapolations to the complete basis set limit using new all-electron correlation consistent basis sets. The latter was carried out with the third-order Douglas-Kroll-Hess Hamiltonian. Correlation down through the 5s5p5d electrons has been taken into account, as well as contributions to the IPs due to the Lamb shift. Spin-orbit coupling contributions calculated at the 4-component Kramers restricted configuration interaction level, as well as the Gaunt term computed at the Dirac-Hartree-Fock level, were added to the best scalar relativistic results. The final ionization potentials are expected to be accurate to at least 5 kcal/mol (0.2 eV) and thus more reliable than the current experimental values of IP{sub 3} through IP{sub 6}.

  18. Probing calculated O 2 + potential curves with an XUV-IR pump-probe experiment

    NASA Astrophysics Data System (ADS)

    Coerlin, Philipp; Fischer, Andreas; Schoenwald, Michael; Sperl, Alexander; Mizuno, Tomoya; Pfeifer, Thomas; Moshammer, Robert; Thumm, Uwe

    2015-05-01

    We study dissociative photo-ionization of O2 in a kinematically complete XUV-IR pump-probe experiment, preparing a vibrational wave packet in the potential of the binding O2+(a4Πu)state by ionization with a single XUV photon. After a variable time-delay the wave packet is promoted to the repulsive O2+(f4Πg)state by a weak IR probe pulse. Comparing the results of a coupled-channel simulation with the experimental kinetic-energy-release and quantum-beat spectra, we are able to discriminate between the adiabatic O2+potential-energy curves (PECs) calculated by. The overall agreement between simulated and experimental results is good; however, not all features of the experimental spectra could be reproduced using these PECs. Using a Morse potential adjusted to the experimental data instead, most features of the experimental spectra are well reproduced by our simulation. This optimized Morse potential is remarkably similar to the theoretically predicted PECs, demonstrating the sensitivity of our experimental method to small changes in the shape of the binding potential. Supported by the DoE, NSF, and Alexander von Humboldt foundation.

  19. Induced Seismicity Potential of Energy Technologies

    NASA Astrophysics Data System (ADS)

    Hitzman, Murray

    2013-03-01

    Earthquakes attributable to human activities-``induced seismic events''-have received heightened public attention in the United States over the past several years. Upon request from the U.S. Congress and the Department of Energy, the National Research Council was asked to assemble a committee of experts to examine the scale, scope, and consequences of seismicity induced during fluid injection and withdrawal associated with geothermal energy development, oil and gas development, and carbon capture and storage (CCS). The committee's report, publicly released in June 2012, indicates that induced seismicity associated with fluid injection or withdrawal is caused in most cases by change in pore fluid pressure and/or change in stress in the subsurface in the presence of faults with specific properties and orientations and a critical state of stress in the rocks. The factor that appears to have the most direct consequence in regard to induced seismicity is the net fluid balance (total balance of fluid introduced into or removed from the subsurface). Energy technology projects that are designed to maintain a balance between the amount of fluid being injected and withdrawn, such as most oil and gas development projects, appear to produce fewer seismic events than projects that do not maintain fluid balance. Major findings from the study include: (1) as presently implemented, the process of hydraulic fracturing for shale gas recovery does not pose a high risk for inducing felt seismic events; (2) injection for disposal of waste water derived from energy technologies does pose some risk for induced seismicity, but very few events have been documented over the past several decades relative to the large number of disposal wells in operation; and (3) CCS, due to the large net volumes of injected fluids suggested for future large-scale carbon storage projects, may have potential for inducing larger seismic events.

  20. Ab initio calculations, potential representation and vibrational dynamics of He2Br2 van der Waals complex.

    PubMed

    Valdés, Alvaro; Prosmiti, Rita; Villarreal, Pablo; Delgado-Barrio, Gerardo

    2005-01-22

    An intermolecular potential energy surface for He(2)Br(2) complex in the ground state is calculated at the levels of fourth-order (MP4) Moller-Plesset and coupled-cluster [CCSD(T)] approximations, using large-core pseudopotential for Br atoms and the aug-cc-pV5Z basis set for He. The surface is characterized by three minima and the minimum energy pathways through them. The global minimum corresponds to a linear He-Br(2)-He configuration, while the two other ones to "police-nightstick" and tetrahedral structures. The corresponding well depths are -90.39/-89.18, -81.23/-80.78 and -74.40/-74.02 cm(-1), respectively, at MP4/CCSD(T) levels of theory. It is found that results obtained by summing three-body parametrized HeBr(2) interactions and the He-He interaction are in very good accord with the corresponding MP4/CSSD(T) configuration energies of the He(2)Br(2). Variational calculations using a sum of three-body interactions are presented to study the bound states of the vdW He(2)Br(2) complex. The binding energy D(0) and the corresponding vibrationally averaged structure are determined for different isomers of the cluster and their comparison with the available experimental data is discussed.

  1. Effective Potential Energies and Transport Cross Sections for Atom-Molecule Interactions of Nitrogen and Nitrogen

    NASA Technical Reports Server (NTRS)

    Stallcop, James R.; Partridge, Harry; Levin, Eugene; Arnold, Jim (Technical Monitor)

    2001-01-01

    The potential energy surfaces for H2-N and N2-N interactions are calculated by accurate ab initio methods and applied to determine transport data. The results confirm that an effective potential energy for accurately determining transport properties can be calculated using a single orientation. A simple method is developed to determine the dispersion coefficients of effective potential energies Effective potential energies required for O2-O collisions are determ=ined. The H2-N, N2-N, O2-H, and O2-O collision integrals are calculated and tabulated for a large range of temperatures. The theoretical values of the N2-N and O2-O diffusion coefficients compare well with measured data available at room temperature.

  2. Efficient characterization of stationary points on potential energy surfaces

    NASA Astrophysics Data System (ADS)

    Deglmann, Peter; Furche, Filipp

    2002-12-01

    Traditional methods for characterizing an optimized molecular structure as a minimum or as a saddle point on the nuclear potential energy surface require the full Hessian. However, if f denotes the number of nuclear degrees of freedom, a full Hessian calculation is more expensive than a single point geometry optimization step by the order of magnitude of f. Here we present a method which allows to determine the lowest vibrational frequencies of a molecule at significantly lower cost. Our approach takes advantage of the fact that only a few perturbed first-order wave functions need to be computed in an iterative diagonalization scheme instead of f ones in a full Hessian calculation. We outline an implementation for Hartree-Fock and density functional methods. Applications indicate a scaling similar to that of a single point energy or gradient calculation, but with a larger prefactor. Depending on the number of soft vibrational modes, the iterative method becomes effective for systems with more than 30-50 atoms.

  3. Communication: Certifying the potential energy landscape

    NASA Astrophysics Data System (ADS)

    Mehta, Dhagash; Hauenstein, Jonathan D.; Wales, David J.

    2013-05-01

    It is highly desirable for numerical approximations to stationary points for a potential energy landscape to lie in the corresponding quadratic convergence basin. However, it is possible that an approximation may lie only in the linear convergence basin, or even in a chaotic region, and hence not converge to the actual stationary point when further optimization is attempted. Proving that a numerical approximation will quadratically converge to the associated stationary point is termed certification. Here, we apply Smale's α-theory to stationary points, providing a certification serving as a mathematical proof that the numerical approximation does indeed correspond to an actual stationary point, independent of the precision employed. As a practical example, employing recently developed certification algorithms, we show how the α-theory can be used to certify all the known minima and transition states of Lennard-Jones LJN atomic clusters for N = 7, …, 14.

  4. Certification and the potential energy landscape

    NASA Astrophysics Data System (ADS)

    Mehta, Dhagash; Hauenstein, Jonathan D.; Wales, David J.

    2014-06-01

    Typically, there is no guarantee that a numerical approximation obtained using standard nonlinear equation solvers is indeed an actual solution, meaning that it lies in the quadratic convergence basin. Instead, it may lie only in the linear convergence basin, or even in a chaotic region, and hence not converge to the corresponding stationary point when further optimization is attempted. In some cases, these non-solutions could be misleading. Proving that a numerical approximation will quadratically converge to a stationary point is termed certification. In this report, we provide details of how Smale's α-theory can be used to certify numerically obtained stationary points of a potential energy landscape, providing a mathematical proof that the numerical approximation does indeed correspond to an actual stationary point, independent of the precision employed.

  5. Tensor decomposition in potential energy surface representations.

    PubMed

    Ostrowski, Lukas; Ziegler, Benjamin; Rauhut, Guntram

    2016-09-14

    In order to reduce the operation count in vibration correlation methods, e.g., vibrational configuration interaction (VCI) theory, a tensor decomposition approach has been applied to the analytical representations of multidimensional potential energy surfaces (PESs). It is shown that a decomposition of the coefficients within the individual n-mode coupling terms in a multimode expansion of the PES is feasible and allows for convenient contractions of one-dimensional integrals with these newly determined factor matrices. Deviations in the final VCI frequencies of a set of small molecules were found to be negligible once the rank of the factors matrices is chosen appropriately. Recommendations for meaningful ranks are provided and different algorithms are discussed. PMID:27634247

  6. Certification and the potential energy landscape

    SciTech Connect

    Mehta, Dhagash; Hauenstein, Jonathan D.; Wales, David J.

    2014-06-14

    Typically, there is no guarantee that a numerical approximation obtained using standard nonlinear equation solvers is indeed an actual solution, meaning that it lies in the quadratic convergence basin. Instead, it may lie only in the linear convergence basin, or even in a chaotic region, and hence not converge to the corresponding stationary point when further optimization is attempted. In some cases, these non-solutions could be misleading. Proving that a numerical approximation will quadratically converge to a stationary point is termed certification. In this report, we provide details of how Smale's α-theory can be used to certify numerically obtained stationary points of a potential energy landscape, providing a mathematical proof that the numerical approximation does indeed correspond to an actual stationary point, independent of the precision employed.

  7. Microscopically derived potential energy surfaces from mostly structural considerations

    NASA Astrophysics Data System (ADS)

    Ermamatov, M. J.; Hess, Peter O.

    2016-08-01

    A simple procedure to estimate the quadrupole Potential-Energy-Surface (PES) is presented, using mainly structural information, namely the content of the shell model space and the Pauli exclusion principle. Further microscopic properties are implicitly contained through the use of results from the Möller and Nix tables or experimental information. A mapping to the geometric potential is performed yielding the PES. The General Collective Model is used in order to obtain an estimate on the spectrum and quadrupole transitions, adjusting only the mass parameter. First, we test the conjecture on known nuclei, deriving the PES and compare them to known data. We will see that the PES approximates very well the structure expected. Having acquired a certain confidence, we predict the PES of several chain of isotopes of heavy and super-heavy nuclei and at the end we investigate the structure of nuclei in the supposed island of stability. One of the main points to show is that simple assumptions can provide already important information on the structure of nuclei outside known regions and that spectra and electromagnetic transitions can be estimated without using involved calculations and assumptions. The procedure does not allow to calculate binding energies. The method presented can be viewed as a starting point for further improvements.

  8. Modification of a new potential model used for calculation of the second virial coefficient and zero density transport properties

    NASA Astrophysics Data System (ADS)

    Parsafar, G. A.; Shokouhi, M.

    A new hard-core potential model was recently used to calculate thermodynamic properties of some model fluids, including equilibrium properties, such as compressibility factor and internal energy. A Lennard-Jones (LJ) like potential has been used to modify the repulsive part of the potential. The modified potential contains five parameters, namely, α, R, ɛ, σ, and σHS. The parameter α is the tail of the attractive branch whose value changes from zero to one. In this work, we have chosen α = 1 to make the potential continuous at separation r = Rσ, where the parameter R is the well width. R lies in the range 1.2 to 2.5, and R = 1.3 was found to be the best value for all real gases studied. The parameter ɛ is the well depth of potential function, and σ is the separation at which the potential function is zero. σHS is the effective hard sphere diameter, which depends on temperature and an additional parameter. Using statistical mechanics along with the Boltzmann factor criterion (BFC) for the effective hard sphere diameter, an analytical expression has been derived for the reduced second virial coefficient in terms of the reduced temperature. Fitting experimental data to expression derived for the second virial coefficient, the potential parameters ɛ and σ are obtained. Since this potential is spherical (depending only on distance), three types of species are chosen, namely Ar and He (monoatomic), N2and O2 (diatomic), and methane (spherical molecule), to show how appropriate this potential model is for them. This model predicts an inversion temperature for the second virial coefficient (temperature at which the second virial coefficient pass through a maximum) at ILM0001, where T1 is the inversion temperature, and TB is the Boyle temperature. The predicted value is better than that of the L-J model (for which ILM0002). The maximum percentage deviation of the second virial coefficient is about 2%, except around the Boyle temperature. Then the transport

  9. The Wind Energy Potential of Kurdistan, Iran.

    PubMed

    Arefi, Farzad; Moshtagh, Jamal; Moradi, Mohammad

    2014-01-01

    In the current work by using statistical methods and available software, the wind energy assessment of prone regions for installation of wind turbines in, Qorveh, has been investigated. Information was obtained from weather stations of Baneh, Bijar, Zarina, Saqez, Sanandaj, Qorveh, and Marivan. The monthly average and maximum of wind speed were investigated between the years 2000-2010 and the related curves were drawn. The Golobad curve (direction and percentage of dominant wind and calm wind as monthly rate) between the years 1997-2000 was analyzed and drawn with plot software. The ten-minute speed (at 10, 30, and 60 m height) and direction (at 37.5 and 10 m height) wind data were collected from weather stations of Iranian new energy organization. The wind speed distribution during one year was evaluated by using Weibull probability density function (two-parametrical), and the Weibull curve histograms were drawn by MATLAB software. According to the average wind speed of stations and technical specifications of the types of turbines, the suitable wind turbine for the station was selected. Finally, the Divandareh and Qorveh sites with favorable potential were considered for installation of wind turbines and construction of wind farms.

  10. The Wind Energy Potential of Kurdistan, Iran

    PubMed Central

    Arefi, Farzad; Moshtagh, Jamal; Moradi, Mohammad

    2014-01-01

    In the current work by using statistical methods and available software, the wind energy assessment of prone regions for installation of wind turbines in, Qorveh, has been investigated. Information was obtained from weather stations of Baneh, Bijar, Zarina, Saqez, Sanandaj, Qorveh, and Marivan. The monthly average and maximum of wind speed were investigated between the years 2000–2010 and the related curves were drawn. The Golobad curve (direction and percentage of dominant wind and calm wind as monthly rate) between the years 1997–2000 was analyzed and drawn with plot software. The ten-minute speed (at 10, 30, and 60 m height) and direction (at 37.5 and 10 m height) wind data were collected from weather stations of Iranian new energy organization. The wind speed distribution during one year was evaluated by using Weibull probability density function (two-parametrical), and the Weibull curve histograms were drawn by MATLAB software. According to the average wind speed of stations and technical specifications of the types of turbines, the suitable wind turbine for the station was selected. Finally, the Divandareh and Qorveh sites with favorable potential were considered for installation of wind turbines and construction of wind farms. PMID:27355042

  11. Thermophotovoltaic energy conversion: Technology and market potential

    NASA Astrophysics Data System (ADS)

    Ostrowski, Leon J.; Pernisz, Udo C.; Fraas, Lewis M.

    1996-02-01

    This report contains material displayed on poster panels during the Conference. The purpose of the contribution was to present a summary of the business overview of thermophotovoltaic generation of electricity and its market potential. The market analysis has shown that the TPV market, while currently still in an early nucleation phase, is evolving into a range of small niche markets out of which larger-size opportunities can emerge. Early commercial applications on yachts and recreational vehicles which require a quiet and emission-free compact electrical generator fit the current TPV technology and economics. Follow-on residential applications are attractive since they can combine generation of electricity with space and hot water heating in a co-generation system. Development of future markets in transportation, both private and communal or industrial, will be driven by legislation requiring emission-free vehicles, and by a reduction in TPV systems cost. As a result of ``moving down the learning curve,'' growing power and consumer markets are predicted to come into reach of TPV systems, a development favored by high overall energy conversion efficiency due to high radiation energy density and to high electric conversion efficiency available with photovoltaic cells.

  12. The Wind Energy Potential of Kurdistan, Iran.

    PubMed

    Arefi, Farzad; Moshtagh, Jamal; Moradi, Mohammad

    2014-01-01

    In the current work by using statistical methods and available software, the wind energy assessment of prone regions for installation of wind turbines in, Qorveh, has been investigated. Information was obtained from weather stations of Baneh, Bijar, Zarina, Saqez, Sanandaj, Qorveh, and Marivan. The monthly average and maximum of wind speed were investigated between the years 2000-2010 and the related curves were drawn. The Golobad curve (direction and percentage of dominant wind and calm wind as monthly rate) between the years 1997-2000 was analyzed and drawn with plot software. The ten-minute speed (at 10, 30, and 60 m height) and direction (at 37.5 and 10 m height) wind data were collected from weather stations of Iranian new energy organization. The wind speed distribution during one year was evaluated by using Weibull probability density function (two-parametrical), and the Weibull curve histograms were drawn by MATLAB software. According to the average wind speed of stations and technical specifications of the types of turbines, the suitable wind turbine for the station was selected. Finally, the Divandareh and Qorveh sites with favorable potential were considered for installation of wind turbines and construction of wind farms. PMID:27355042

  13. Stabilized quasi-Newton optimization of noisy potential energy surfaces

    NASA Astrophysics Data System (ADS)

    Schaefer, Bastian; Ghasemi, S. Alireza; Roy, Shantanu; Goedecker, Stefan; Goedecker Group Team

    Optimizations of atomic positions belong to the most frequently performed tasks in electronic structure calculations. Many simulations like global minimum searches or the identification of chemical reaction pathways can require the computation of hundreds or thousands of minimizations or saddle points. To automatize these tasks, optimization algorithms must not only be efficient but also very reliable. Unfortunately, computational noise in forces and energies is inherent to electronic structure codes. This computational noise poses a severe problem to the stability of efficient optimization methods like the limited-memory Broyden-Fletcher-Goldfarb-Shanno algorithm. In this talk a recently published technique that allows to obtain significant curvature information of noisy potential energy surfaces is presented. This technique was used to construct both, a stabilized quasi-Newton minimization method and a stabilized quasi-Newton saddle finding approach. With the help of benchmarks both the minimizer and the saddle finding approach were demonstrated to be superior to comparable existing methods.

  14. Stabilized quasi-Newton optimization of noisy potential energy surfaces

    SciTech Connect

    Schaefer, Bastian; Goedecker, Stefan; Alireza Ghasemi, S.; Roy, Shantanu

    2015-01-21

    Optimizations of atomic positions belong to the most commonly performed tasks in electronic structure calculations. Many simulations like global minimum searches or characterizations of chemical reactions require performing hundreds or thousands of minimizations or saddle computations. To automatize these tasks, optimization algorithms must not only be efficient but also very reliable. Unfortunately, computational noise in forces and energies is inherent to electronic structure codes. This computational noise poses a severe problem to the stability of efficient optimization methods like the limited-memory Broyden–Fletcher–Goldfarb–Shanno algorithm. We here present a technique that allows obtaining significant curvature information of noisy potential energy surfaces. We use this technique to construct both, a stabilized quasi-Newton minimization method and a stabilized quasi-Newton saddle finding approach. We demonstrate with the help of benchmarks that both the minimizer and the saddle finding approach are superior to comparable existing methods.

  15. Stabilized quasi-Newton optimization of noisy potential energy surfaces.

    PubMed

    Schaefer, Bastian; Alireza Ghasemi, S; Roy, Shantanu; Goedecker, Stefan

    2015-01-21

    Optimizations of atomic positions belong to the most commonly performed tasks in electronic structure calculations. Many simulations like global minimum searches or characterizations of chemical reactions require performing hundreds or thousands of minimizations or saddle computations. To automatize these tasks, optimization algorithms must not only be efficient but also very reliable. Unfortunately, computational noise in forces and energies is inherent to electronic structure codes. This computational noise poses a severe problem to the stability of efficient optimization methods like the limited-memory Broyden-Fletcher-Goldfarb-Shanno algorithm. We here present a technique that allows obtaining significant curvature information of noisy potential energy surfaces. We use this technique to construct both, a stabilized quasi-Newton minimization method and a stabilized quasi-Newton saddle finding approach. We demonstrate with the help of benchmarks that both the minimizer and the saddle finding approach are superior to comparable existing methods.

  16. Energy resource potential of natural gas hydrates

    USGS Publications Warehouse

    Collett, T.S.

    2002-01-01

    The discovery of large gas hydrate accumulations in terrestrial permafrost regions of the Arctic and beneath the sea along the outer continental margins of the world's oceans has heightened interest in gas hydrates as a possible energy resource. However, significant to potentially insurmountable technical issues must be resolved before gas hydrates can be considered a viable option for affordable supplies of natural gas. The combined information from Arctic gas hydrate studies shows that, in permafrost regions, gas hydrates may exist at subsurface depths ranging from about 130 to 2000 m. The presence of gas hydrates in offshore continental margins has been inferred mainly from anomalous seismic reflectors, known as bottom-simulating reflectors, that have been mapped at depths below the sea floor ranging from about 100 to 1100 m. Current estimates of the amount of gas in the world's marine and permafrost gas hydrate accumulations are in rough accord at about 20,000 trillion m3. Disagreements over fundamental issues such as the volume of gas stored within delineated gas hydrate accumulations and the concentration of gas hydrates within hydrate-bearing strata have demonstrated that we know little about gas hydrates. Recently, however, several countries, including Japan, India, and the United States, have launched ambitious national projects to further examine the resource potential of gas hydrates. These projects may help answer key questions dealing with the properties of gas hydrate reservoirs, the design of production systems, and, most important, the costs and economics of gas hydrate production.

  17. Development of a "First Principles" Water Potential with Flexible Monomers: Dimer Potential Energy Surface, VRT Spectrum, and Second Virial Coefficient.

    PubMed

    Babin, Volodymyr; Leforestier, Claude; Paesani, Francesco

    2013-12-10

    The development of a "first principles" water potential with flexible monomers (MB-pol) for molecular simulations of water systems from gas to condensed phases is described. MB-pol is built upon the many-body expansion of the intermolecular interactions, and the specific focus of this study is on the two-body term (V2B) representing the full-dimensional intermolecular part of the water dimer potential energy surface. V2B is constructed by fitting 40,000 dimer energies calculated at the CCSD(T)/CBS level of theory and imposing the correct asymptotic behavior at long-range as predicted from "first principles". The comparison of the calculated vibration-rotation tunneling (VRT) spectrum and second virial coefficient with the corresponding experimental results demonstrates the accuracy of the MB-pol dimer potential energy surface.

  18. Multiscale modeling approach for calculating grain-boundary energies from first principles

    SciTech Connect

    Shenderova, O.A.; Brenner, D.W.; Nazarov, A.A.; Romanov, A.E.; Yang, L.H.

    1998-02-01

    A multiscale modeling approach is proposed for calculating energies of tilt-grain boundaries in covalent materials from first principles over an entire misorientation range for given tilt axes. The method uses energies from density-functional calculations for a few key structures as input into a disclination structural-units model. This approach is demonstrated by calculating energies of {l_angle}001{r_angle}-symmetrical tilt-grain boundaries in diamond. {copyright} {ital 1998} {ital The American Physical Society}

  19. A Simplified Confinement Method (SCM) for Calculating Absolute Free Energies and Free Energy and Entropy Differences

    PubMed Central

    Ovchinnikov, Victor; Cecchini, Marco; Karplus, Martin

    2013-01-01

    A simple and robust formulation of the path-independent confinement method for the calculation of free energies is presented. The simplified confinement method (SCM) does not require matrix diagonalization or switching off the molecular force field, and has a simple convergence criterion. The method can be readily implemented in molecular dynamics programs with minimal or no code modifications. Because the confinement method is a special case of thermodynamic integration, it is trivially parallel over the integration variable. The accuracy of the method is demonstrated using a model diatomic molecule, for which exact results can be computed analytically. The method is then applied to the alanine dipeptide in vacuum, and to the α-helix ↔ β-sheet transition in a sixteen-residue peptide modeled in implicit solvent. The SCM requires less effort for the calculation of free energy differences than previous formulations because it does not require computing normal modes. The SCM has a diminished advantage for determining absolute free energy values, because it requires decreasing the MD integration step to obtain accurate results. An approximate confinement procedure is introduced, which can be used to estimate directly the configurational entropy difference between two macrostates, without the need for additional computation of the difference in the free energy or enthalpy. The approximation has similar convergence properties as the standard confinement method for the calculation of free energies. The use of the approximation requires about five times less wall-clock simulation time than that needed to compute enthalpy differences to similar precision from an MD trajectory. For the biomolecular systems considered in this study, the errors in the entropy approximation are under 10%. The approximation will therefore be most useful for cases in which the dominant source of error is insufficient sampling in the estimation of enthalpies, as arises in simulations of large

  20. Potential energy curves and collision integrals of air components

    NASA Technical Reports Server (NTRS)

    Partridge, Harry; Stallcop, James R.; Levin, Eugene; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    Collision integrals are fundamental quantities required to determine the transport properties of the environment surrounding aerospace vehicles in the upper atmosphere. These collision integrals can be determined as a function of temperature from the potential energy curves describing the atomic and molecular collisions. Ab initio calculations provide a practical method of computing the required interaction potentials. In this work we will discuss recent advances with an emphasis on the accuracy that is obtainable. Results for interactions, e.g. N+N, N+O, O+O, and H+N2 will be reviewed and their application to the determination of transport properties, such as diffusion and viscosity coefficients, will be examined.

  1. Quantum chemical calculations of the reorganization energy of blue-copper proteins.

    PubMed Central

    Olsson, M. H.; Ryde, U.; Roos, B. O.

    1998-01-01

    The inner-sphere reorganization energy for several copper complexes related to the active site in blue-copper protein has been calculated with the density functional B3LYP method. The best model of the blue-copper proteins, Cu(Im)2(SCH3)(S(CH3)2)(0/+), has a self-exchange inner-sphere reorganization energy of 62 kJ/mol, which is at least 120 kJ/mol lower than for Cu(H2O)4(+/2+). This lowering of the reorganization energy is caused by the soft ligands in the blue-copper site, especially the cysteine thiolate and the methionine thioether groups. Soft ligands both make the potential surfaces of the complexes flatter and give rise to oxidized structures that are quite close to a tetrahedron (rather than tetragonal). Approximately half of the reorganization energy originates from changes in the copper-ligand bond lengths and half of this contribution comes from the Cu-S(Cys) bond. A tetragonal site, which is present in the rhombic type 1 blue-copper proteins, has a slightly higher (16 kJ/mol) inner-sphere reorganization energy than a trigonal site, present in the axial type 1 copper proteins. A site with the methionine ligand replaced by an amide group, as in stellacyanin, has an even higher reorganization energy, about 90 kJ/mol. PMID:9865961

  2. Transition Metal Oxide Alloys as Potential Solar Energy Conversion Materials

    SciTech Connect

    Toroker, Maytal; Carter, Emily A.

    2013-02-21

    First-row transition metal oxides (TMOs) are inexpensive potentia alternative materials for solar energy conversion devices. However, some TMOs, such as manganese(II) oxide, have band gaps that are too large for efficiently absorbing solar energy. Other TMOs, such as iron(II) oxide, have conduction and valence band edges with the same orbital character that may lead to unfavorably high electron–hole recombination rates. Another limitation of iron(II) oxide is that the calculated valence band edge is not positioned well for oxidizing water. We predict that key properties, including band gaps, band edge positions, and possibly electron–hole recombination rates, may be improved by alloying TMOs that have different band alignments. A new metric, the band gap center offset, is introduced for simple screening of potential parent materials. The concept is illustrated by calculating the electronic structure of binary oxide alloys that contain manganese, nickel, iron, zinc, and/or magnesium, within density functional theory (DFT)+U and hybrid DFT theories. We conclude that alloys of iron(II) oxide are worth evaluating further as solar energy conversion materials.

  3. Spectroscopic and electronic structure calculation of a potential antibacterial agent incorporating pyrido-dipyrimidine-dione moiety using first principles

    NASA Astrophysics Data System (ADS)

    Fatma, Shaheen; Bishnoi, Abha; Singh, Vineeta; Al-Omary, Fatmah A. M.; El-Emam, Ali A.; Pathak, Shilendra; Srivastava, Ruchi; Prasad, Onkar; Sinha, Leena

    2016-04-01

    Quantum chemical calculations of geometrical structure, energy and vibrational wavenumbers of a novel functionalized pyrido-pyrimidine compound (a prospective antibacterial agent), chemically known as 6-Methyl,13,14,15-Trihydro-14-(4-Nitrophenyl)pyrido[1,2-a:1‧,2‧-a‧] pyrido[2″,3″-d:6″,5″-d‧]dipyrimidine-13,15-dione (C24H16N6O4), were carried out, using B3LYP/6311++G(d,p) method. Comprehensive interpretation of the infrared and Raman spectra of the compound under study is based on potential energy distribution. A good coherence between experimental and theoretical wavenumbers shows the preciseness of the assignments. NLO properties like the dipole moment, polarizability, first static hyperpolarizability and molecular electrostatic potential surface have been calculated to get a better cognizance of the properties of the title compound. Molecular docking results reveal that the title compound exhibit inhibitory activity against Staphylococcus aureus.

  4. Molecular dynamics and free energy perturbation calculations on fluorocarbons and aspartyl protease inhibitors

    SciTech Connect

    Gough, C.A.

    1992-01-01

    Molecular dynamics (MD) simulations of pure tetrafluoromethane and trifluoromethane were performed to determine the van der Waals parameters R[sup *] and [epsilon] for fluorine and for the hydrogen of trifluoromethane. The best values of R[sup *] and [epsilon] for fluorine were determined to be 1.75 [angstrom] and 0.061 kcal/mole. For the hydrogen, the optimal R[sup *] and [epsilon] were determined to be 1.21 [angstrom] and 0.015 kcal/mole. The relative free energies of aqueous solvation of several fluorinated derivatives of methane were calculated using the FEP method. The calculations duplicated the experimental free energies relatively well, but the calculation of the bond-potential of mean force (bond-PMF) contribution was necessary in order to get the most satisfactory agreement with experiment. In addition, results of an ethanol-to-ethane perturbation in aqueous solution show that the bond-PMF contribution is important even for FEP calculations not involving large changes in size if the length of a bond is changed during the perturbation. MD simulations were run to determine the structure of the waters solvating fluoromethane, trifluoromethane, and tetrafluoromethane. The calculated radical distribution functions and water orientations suggest that, on average, there is one water-fluorine hydrogen bond in the case of fluoromethane. In contrast, there is no evidence of water-flourine hydrogen-bonding in the cases of trifluoromethane or tetrafluoromethane. These results suggest that the greater aqueous solubility of fluromethane relative to trifluoromethane is largely due to the poorer quality of the water-fluorine electrostatic interactions in trifluoromethane.

  5. Age difference in numeral recognition and calculation: an event-related potential study.

    PubMed

    Xuan, Dong; Wang, Suhong; Yang, Yilin; Meng, Ping; Xu, Feng; Yang, Wen; Sheng, Wei; Yang, Yuxia

    2007-01-01

    In this study, we investigated the age difference in numeral recognition and calculation in one group of school-aged children (n = 38) and one of undergraduate students (n = 26) using the event-related potential (ERP) methods. Consistent with previous reports, the age difference was significant in behavioral results. Both numeral recognition and calculation elicited a negativity peaking at about 170-280 ms (N2) and a positivity peaking at 200-470 ms (pSW) in raw ERPs, and a difference potential (dN3) between 360 and 450 ms. The difference between the two age groups indicated that more attention resources were devoted to arithmetical tasks in school-aged children, and that school-aged children and undergraduate students appear to use different strategies to solve arithmetical problems. The analysis of frontal negativity suggested that numeral recognition and mental calculation impose greater load on working memory and executive function in schoolchildren than in undergraduate students. The topography data determined that the parietal regions were responsible for arithmetical function in humans, and there was an age-related difference in the area of cerebral activation. PMID:17364561

  6. CALCULATING POINT-CHARGE WAKEFIELDS FROM FINITE LENGTH BUNCH WAKE-POTENTIALS

    SciTech Connect

    Podobedov, B.; Stupakov, G.

    2011-03-28

    Starting from analytical properties of high frequency geometric impedance we show how one can accurately calculate short bunch wake-potentials (and even point-charge wakefields) from time domain calculations performed with a much longer bunch. In many practical instances this drastically reduces the need for computer resources, speeds up the calculations, and improves their accuracy. To illustrate this method we give examples for 2D accelerator structures of various complexities. We describe preliminary results of a new method that allows us to accurately obtain longitudinal wakefields of short bunches by adding a long-bunch result from an EM solver and a singular analytical wake model. In the future this work will be generalized to 3D geometries as well. Similarly, the method should be equally applicable to the calculations of transverse wakefields. Periodic structures with a significant number of periods (2 {ge} a{sup 2}/{sigma}L, where L is the period length) have not been considered so far. They have asymptotic wakefields that differ from the examples described above. We believe this method is applicable to such geometries as well, as long as correct asymptotic solutions are used.

  7. Calculation of Water Drop Trajectories to and About Arbitrary Three-Dimensional Bodies in Potential Airflow

    NASA Technical Reports Server (NTRS)

    Norment, H. G.

    1980-01-01

    Calculations can be performed for any atmospheric conditions and for all water drop sizes, from the smallest cloud droplet to large raindrops. Any subsonic, external, non-lifting flow can be accommodated; flow into, but not through, inlets also can be simulated. Experimental water drop drag relations are used in the water drop equations of motion and effects of gravity settling are included. Seven codes are described: (1) a code used to debug and plot body surface description data; (2) a code that processes the body surface data to yield the potential flow field; (3) a code that computes flow velocities at arrays of points in space; (4) a code that computes water drop trajectories from an array of points in space; (5) a code that computes water drop trajectories and fluxes to arbitrary target points; (6) a code that computes water drop trajectories tangent to the body; and (7) a code that produces stereo pair plots which include both the body and trajectories. Code descriptions include operating instructions, card inputs and printouts for example problems, and listing of the FORTRAN codes. Accuracy of the calculations is discussed, and trajectory calculation results are compared with prior calculations and with experimental data.

  8. Calculation of subsonic and supersonic steady and unsteady aerodynamic forces using velocity potential aerodynamic elements

    NASA Technical Reports Server (NTRS)

    Haviland, J. K.; Yoo, Y. S.

    1976-01-01

    Expressions for calculation of subsonic and supersonic, steady and unsteady aerodynamic forces are derived, using the concept of aerodynamic elements applied to the downwash velocity potential method. Aerodynamic elements can be of arbitrary out of plane polygon shape, although numerical calculations are restricted to rectangular elements, and to the steady state case in the supersonic examples. It is suggested that the use of conforming, in place of rectangular elements, would give better results. Agreement with results for subsonic oscillating T tails is fair, but results do not converge as the number of collocation points is increased. This appears to be due to the form of expression used in the calculations. The methods derived are expected to facilitate automated flutter analysis on the computer. In particular, the aerodynamic element concept is consistent with finite element methods already used for structural analysis. The method is universal for the complete Mach number range, and, finally, the calculations can be arranged so that they do not have to be repeated completely for every reduced frequency.

  9. An ab initio method for locating potential energy minima

    SciTech Connect

    Bock, Nicolas; Peery, Travis; Venneri, Giulia; Chisolm, Eric; Wallace, Duane; Lizarraga, Raquel; Holmstrom, Erik

    2009-01-01

    We study the potential energy landscape underlying the motion of monatomic liquids by quenching from random initial configurations (stochastic configurations) to the nearest local minimum of the potential energy. We show that this procedure reveals the underlying potential energy surface directly. This is in contrast to the common technique of quenching from a molecular dynamics trajectory which does not allow a direct view of the underlying potential energy surface, but needs to be corrected for thermodynamic weighting factors.

  10. Energy from CO2 using capacitive electrodes--theoretical outline and calculation of open circuit voltage.

    PubMed

    Paz-Garcia, J M; Schaetzle, O; Biesheuvel, P M; Hamelers, H V M

    2014-03-15

    Recently, a new technology has been proposed for the utilization of energy from CO2 emissions (Hamelers et al., 2014). The principle consists of controlling the dilution process of CO2-concentrated gas (e.g., exhaust gas) into CO2-dilute gas (e.g., air) thereby extracting a fraction of the released mixing energy. In this paper, we describe the theoretical fundamentals of this technology when using a pair of charge-selective capacitive electrodes. We focus on the behavior of the chemical system consisting of CO2 gas dissolved in water or monoethanolamine solution. The maximum voltage given for the capacitive cell is theoretically calculated, based on the membrane potential. The different aspects that affect this theoretical maximum value are discussed.

  11. Impact of dietary fiber energy on the calculation of food total energy value in the Brazilian Food Composition Database.

    PubMed

    Menezes, Elizabete Wenzel de; Grande, Fernanda; Giuntini, Eliana Bistriche; Lopes, Tássia do Vale Cardoso; Dan, Milana Cara Tanasov; Prado, Samira Bernardino Ramos do; Franco, Bernadette Dora Gombossy de Melo; Charrondière, U Ruth; Lajolo, Franco Maria

    2016-02-15

    Dietary fiber (DF) contributes to the energy value of foods and including it in the calculation of total food energy has been recommended for food composition databases. The present study aimed to investigate the impact of including energy provided by the DF fermentation in the calculation of food energy. Total energy values of 1753 foods from the Brazilian Food Composition Database were calculated with or without the inclusion of DF energy. The energy values were compared, through the use of percentage difference (D%), in individual foods and in daily menus. Appreciable energy D% (⩾10) was observed in 321 foods, mainly in the group of vegetables, legumes and fruits. However, in the Brazilian typical menus containing foods from all groups, only D%<3 was observed. In mixed diets, the DF energy may cause slight variations in total energy; on the other hand, there is appreciable energy D% for certain foods, when individually considered.

  12. Free energy calculations, enhanced by a Gaussian ansatz, for the "chemical work" distribution.

    PubMed

    Boulougouris, Georgios C

    2014-05-15

    The evaluation of the free energy is essential in molecular simulation because it is intimately related with the existence of multiphase equilibrium. Recently, it was demonstrated that it is possible to evaluate the Helmholtz free energy using a single statistical ensemble along an entire isotherm by accounting for the "chemical work" of transforming each molecule, from an interacting one, to an ideal gas. In this work, we show that it is possible to perform such a free energy perturbation over a liquid vapor phase transition. Furthermore, we investigate the link between a general free energy perturbation scheme and the novel nonequilibrium theories of Crook's and Jarzinsky. We find that for finite systems away from the thermodynamic limit the second law of thermodynamics will always be an inequality for isothermal free energy perturbations, resulting always to a dissipated work that may tend to zero only in the thermodynamic limit. The work, the heat, and the entropy produced during a thermodynamic free energy perturbation can be viewed in the context of the Crooks and Jarzinsky formalism, revealing that for a given value of the ensemble average of the "irreversible" work, the minimum entropy production corresponded to a Gaussian distribution for the histogram of the work. We propose the evaluation of the free energy difference in any free energy perturbation based scheme on the average irreversible "chemical work" minus the dissipated work that can be calculated from the variance of the distribution of the logarithm of the work histogram, within the Gaussian approximation. As a consequence, using the Gaussian ansatz for the distribution of the "chemical work," accurate estimates for the chemical potential and the free energy of the system can be performed using much shorter simulations and avoiding the necessity of sampling the computational costly tails of the "chemical work." For a more general free energy perturbation scheme that the Gaussian ansatz may not be

  13. Alternative definitions of the frozen energy in energy decomposition analysis of density functional theory calculations.

    PubMed

    Horn, Paul R; Head-Gordon, Martin

    2016-02-28

    In energy decomposition analysis (EDA) of intermolecular interactions calculated via density functional theory, the initial supersystem wavefunction defines the so-called "frozen energy" including contributions such as permanent electrostatics, steric repulsions, and dispersion. This work explores the consequences of the choices that must be made to define the frozen energy. The critical choice is whether the energy should be minimized subject to the constraint of fixed density. Numerical results for Ne2, (H2O)2, BH3-NH3, and ethane dissociation show that there can be a large energy lowering associated with constant density orbital relaxation. By far the most important contribution is constant density inter-fragment relaxation, corresponding to charge transfer (CT). This is unwanted in an EDA that attempts to separate CT effects, but it may be useful in other contexts such as force field development. An algorithm is presented for minimizing single determinant energies at constant density both with and without CT by employing a penalty function that approximately enforces the density constraint.

  14. Alternative definitions of the frozen energy in energy decomposition analysis of density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Horn, Paul R.; Head-Gordon, Martin

    2016-02-01

    In energy decomposition analysis (EDA) of intermolecular interactions calculated via density functional theory, the initial supersystem wavefunction defines the so-called "frozen energy" including contributions such as permanent electrostatics, steric repulsions, and dispersion. This work explores the consequences of the choices that must be made to define the frozen energy. The critical choice is whether the energy should be minimized subject to the constraint of fixed density. Numerical results for Ne2, (H2O)2, BH3-NH3, and ethane dissociation show that there can be a large energy lowering associated with constant density orbital relaxation. By far the most important contribution is constant density inter-fragment relaxation, corresponding to charge transfer (CT). This is unwanted in an EDA that attempts to separate CT effects, but it may be useful in other contexts such as force field development. An algorithm is presented for minimizing single determinant energies at constant density both with and without CT by employing a penalty function that approximately enforces the density constraint.

  15. An analytical model for the calculation of the change in transmembrane potential produced by an ultrawideband electromagnetic pulse.

    PubMed

    Hart, Francis X; Easterly, Clay E

    2004-05-01

    The electric field pulse shape and change in transmembrane potential produced at various points within a sphere by an intense, ultrawideband pulse are calculated in a four stage, analytical procedure. Spheres of two sizes are used to represent the head of a human and the head of a rat. In the first stage, the pulse is decomposed into its Fourier components. In the second stage, Mie scattering analysis (MSA) is performed for a particular point in the sphere on each of the Fourier components, and the resulting electric field pulse shape is obtained for that point. In the third stage, the long wavelength approximation (LWA) is used to obtain the change in transmembrane potential in a cell at that point. In the final stage, an energy analysis is performed. These calculations are performed at 45 points within each sphere. Large electric fields and transmembrane potential changes on the order of a millivolt are produced within the brain, but on a time scale on the order of nanoseconds. The pulse shape within the brain differs considerably from that of the incident pulse. Comparison of the results for spheres of different sizes indicates that scaling of such pulses across species is complicated. PMID:15114634

  16. Energy levels of isoelectronic impurities by large scale LDA calculations

    SciTech Connect

    Li, Jingbo; Wang, Lin-Wang

    2002-11-22

    Isoelectronic impurity states are localized states induced by stoichiometric single atom substitution in bulk semiconductor. Photoluminescence spectra indicate deep impurity levels of 0.5 to 0.9eV above the top of valence band for systems like: GaN:As, GaN:P, CdS:Te, ZnS:Te. Previous calculations based on small supercells seemingly confirmed these experimental results. However, the current ab initio calculations based on thousand atom supercells indicate that the impurity levels of the above systems are actually much shallower(0.04 to 0.23 eV), and these impurity levels should be compared with photoluminescence excitation spectra, not photoluminescence spectra.

  17. Distributed Multipolar Expansion Approach to Calculation of Excitation Energy Transfer Couplings.

    PubMed

    Błasiak, Bartosz; Maj, Michał; Cho, Minhaeng; Góra, Robert W

    2015-07-14

    We propose a new approach for estimating the electrostatic part of the excitation energy transfer (EET) coupling between electronically excited chromophores based on the transition density-derived cumulative atomic multipole moments (TrCAMM). In this approach, the transition potential of a chromophore is expressed in terms of truncated distributed multipolar expansion and analytical formulas for the TrCAMMs are derived. The accuracy and computational feasibility of the proposed approach is tested against the exact Coulombic couplings, and various multipole expansion truncation schemes are analyzed. The results of preliminary calculations show that the TrCAMM approach is capable of reproducing the exact Coulombic EET couplings accurately and efficiently and is superior to other widely used schemes: the transition charges from electrostatic potential (TrESP) and the transition density cube (TDC) method.

  18. Examining fine potential energy effects in high-energy fission dynamics

    NASA Astrophysics Data System (ADS)

    Mazurek, K.; Schmitt, C.; Nadtochy, P. N.; Kmiecik, M.; Maj, A.; Wasiak, P.; Wieleczko, J. P.

    2013-11-01

    The potential energy surface plays a decisive role in nuclear fission. Together with inertia and viscosity, it influences the trajectory of the system, and the properties of the fission fragments result from the puzzling interplay between static and dynamical effects. A careful study on the influence of the parametrization of the potential energy landscape in heavy-ion-induced fission is performed. Dynamical calculations are done within the stochastic Langevin approach in a three-dimensional deformation space. Various prescriptions of the potential energy surface are considered, probing two different Liquid Drop models and the deformation dependence of the Wigner/congruence energy. A wide set of observables, including cross sections, particle multiplicities, and integral, as well as isotopic and isobaric, distributions of fission and evaporation products, is analyzed. Nuclei close to the Businaro-Gallone point are confirmed to be well suited for investigating the Liquid Drop parametrization, while the influence of the deformation-dependent Wigner/congruence energy is difficult to demonstrate unambiguously in fission at high excitation energies.

  19. Transportation Energy Use and Conservation Potential

    ERIC Educational Resources Information Center

    Hirst, Eric

    1973-01-01

    Analyzes transportation energy consumption and energy intensiveness for inter-city freight and passenger traffic and urban passenger traffic with the definition of energy intensiveness as Btu per ton-mile or per passenger-mile. Indicates that public education is one of three ways to achieve the goals of energy conservation. (CC)

  20. Theoretical studies of potential energy surfaces and computational methods.

    SciTech Connect

    Shepard, R.

    2006-01-01

    This project involves the development, implementation, and application of theoretical methods for the calculation and characterization of potential energy surfaces (PES) involving molecular species that occur in hydrocarbon combustion. These potential energy surfaces require an accurate and balanced treatment of reactants, intermediates, and products. Most of our work focuses on general multiconfiguration self-consistent-field (MCSCF) and multireference single- and double-excitation configuration interaction (MRSDCI) methods. In contrast to the more common single-reference electronic structure methods, this approach is capable of describing accurately molecular systems that are highly distorted away from their equilibrium geometries, including reactant, fragment, and transition-state geometries, and of describing regions of the potential surface that are associated with electronic wave functions of widely varying nature. The MCSCF reference wave functions are designed to be sufficiently flexible to describe qualitatively the changes in the electronic structure over the broad range of molecular geometries of interest. The necessary mixing of ionic, covalent, and Rydberg contributions, along with the appropriate treatment of the different electron-spin components (e.g. closed shell, high-spin open-shell, low-spin open shell, radical, diradical, etc.) of the wave functions are treated correctly at this level. Further treatment of electron correlation effects is included using large scale multireference CI wave functions, particularly including the single and double excitations relative to the MCSCF reference space. This leads to the most flexible and accurate large-scale MRSDCI wave functions that have been used to date in global PES studies.

  1. Theoretical studies of potential energy surfaces and computational methods

    SciTech Connect

    Shepard, R.

    1993-12-01

    This project involves the development, implementation, and application of theoretical methods for the calculation and characterization of potential energy surfaces involving molecular species that occur in hydrocarbon combustion. These potential energy surfaces require an accurate and balanced treatment of reactants, intermediates, and products. This difficult challenge is met with general multiconfiguration self-consistent-field (MCSCF) and multireference single- and double-excitation configuration interaction (MRSDCI) methods. In contrast to the more common single-reference electronic structure methods, this approach is capable of describing accurately molecular systems that are highly distorted away from their equilibrium geometries, including reactant, fragment, and transition-state geometries, and of describing regions of the potential surface that are associated with electronic wave functions of widely varying nature. The MCSCF reference wave functions are designed to be sufficiently flexible to describe qualitatively the changes in the electronic structure over the broad range of geometries of interest. The necessary mixing of ionic, covalent, and Rydberg contributions, along with the appropriate treatment of the different electron-spin components (e.g. closed shell, high-spin open-shell, low-spin open shell, radical, diradical, etc.) of the wave functions, are treated correctly at this level. Further treatment of electron correlation effects is included using large scale multireference CI wave functions, particularly including the single and double excitations relative to the MCSCF reference space. This leads to the most flexible and accurate large-scale MRSDCI wave functions that have been used to date in global PES studies.

  2. Thunderstorm Electric Potential Profiles: Electrical Evolution and Lightning Energy

    NASA Astrophysics Data System (ADS)

    Stolzenburg, M.; Marshall, T. C.

    2005-05-01

    From a balloon sounding of electric field through a thunderstorm, one can calculate the vertical profile of potential, V, within the storm. In this presentation we investigate thunderstorm electrical evolution by examining V profiles through various stages of a storm's life. We present data from New Mexico mountain thunderstorms in which we made a series of 4 to 6 balloon soundings. Several of the successive V profiles in the same storm are quite similar, in spite of the numerous lightning flashes that occurred during the balloon flights. These similarities suggest that the V profiles are reasonable estimates of the in-cloud potential. The similar profiles occur during the mature phase of the storm, and mature phase profiles are even similar from one storm to another. This is true despite different lightning flashing rates and, presumably, different charge generation rates in the different storms. Another result of this work is that potential profiles during the early and late stages of the storm do not resemble those from the mature stage. Recently, Coleman et al. [2003] showed that intra-cloud (IC) flashes connect potential extrema of opposite polarity and that normal (negative) cloud-to-ground (CG) flashes connect a potential minimum to ground. Thus we can use the V profiles to estimate the potential difference spanned by lightning flashes during the evolution of the storm and, with this, estimate the lightning energy. Typical potential differences spanned by IC and CG flashes will be presented from four storms. Reference: Coleman, L.M., T.C. Marshall, M. Stolzenburg, T. Hamlin, P.R. Krehbiel, W. Rison, and R.J. Thomas, Effects of charge and electrostatic potential on lightning propagation, J. Geophys. Res., 108, doi:10.1029/2002JD002718, 2003.

  3. Advanced Potential Energy Surfaces for Molecular Simulation.

    PubMed

    Albaugh, Alex; Boateng, Henry A; Bradshaw, Richard T; Demerdash, Omar N; Dziedzic, Jacek; Mao, Yuezhi; Margul, Daniel T; Swails, Jason; Zeng, Qiao; Case, David A; Eastman, Peter; Wang, Lee-Ping; Essex, Jonathan W; Head-Gordon, Martin; Pande, Vijay S; Ponder, Jay W; Shao, Yihan; Skylaris, Chris-Kriton; Todorov, Ilian T; Tuckerman, Mark E; Head-Gordon, Teresa

    2016-09-22

    Advanced potential energy surfaces are defined as theoretical models that explicitly include many-body effects that transcend the standard fixed-charge, pairwise-additive paradigm typically used in molecular simulation. However, several factors relating to their software implementation have precluded their widespread use in condensed-phase simulations: the computational cost of the theoretical models, a paucity of approximate models and algorithmic improvements that can ameliorate their cost, underdeveloped interfaces and limited dissemination in computational code bases that are widely used in the computational chemistry community, and software implementations that have not kept pace with modern high-performance computing (HPC) architectures, such as multicore CPUs and modern graphics processing units (GPUs). In this Feature Article we review recent progress made in these areas, including well-defined polarization approximations and new multipole electrostatic formulations, novel methods for solving the mutual polarization equations and increasing the MD time step, combining linear-scaling electronic structure methods with new QM/MM methods that account for mutual polarization between the two regions, and the greatly improved software deployment of these models and methods onto GPU and CPU hardware platforms. We have now approached an era where multipole-based polarizable force fields can be routinely used to obtain computational results comparable to state-of-the-art density functional theory while reaching sampling statistics that are acceptable when compared to that obtained from simpler fixed partial charge force fields.

  4. Advanced Potential Energy Surfaces for Molecular Simulation.

    PubMed

    Albaugh, Alex; Boateng, Henry A; Bradshaw, Richard T; Demerdash, Omar N; Dziedzic, Jacek; Mao, Yuezhi; Margul, Daniel T; Swails, Jason; Zeng, Qiao; Case, David A; Eastman, Peter; Wang, Lee-Ping; Essex, Jonathan W; Head-Gordon, Martin; Pande, Vijay S; Ponder, Jay W; Shao, Yihan; Skylaris, Chris-Kriton; Todorov, Ilian T; Tuckerman, Mark E; Head-Gordon, Teresa

    2016-09-22

    Advanced potential energy surfaces are defined as theoretical models that explicitly include many-body effects that transcend the standard fixed-charge, pairwise-additive paradigm typically used in molecular simulation. However, several factors relating to their software implementation have precluded their widespread use in condensed-phase simulations: the computational cost of the theoretical models, a paucity of approximate models and algorithmic improvements that can ameliorate their cost, underdeveloped interfaces and limited dissemination in computational code bases that are widely used in the computational chemistry community, and software implementations that have not kept pace with modern high-performance computing (HPC) architectures, such as multicore CPUs and modern graphics processing units (GPUs). In this Feature Article we review recent progress made in these areas, including well-defined polarization approximations and new multipole electrostatic formulations, novel methods for solving the mutual polarization equations and increasing the MD time step, combining linear-scaling electronic structure methods with new QM/MM methods that account for mutual polarization between the two regions, and the greatly improved software deployment of these models and methods onto GPU and CPU hardware platforms. We have now approached an era where multipole-based polarizable force fields can be routinely used to obtain computational results comparable to state-of-the-art density functional theory while reaching sampling statistics that are acceptable when compared to that obtained from simpler fixed partial charge force fields. PMID:27513316

  5. Mie potentials for phase equilibria calculations: application to alkanes and perfluoroalkanes.

    PubMed

    Potoff, Jeffrey J; Bernard-Brunel, Damien A

    2009-11-01

    Transferable united-atom force fields, based on n - 6 Lennard-Jones potentials, are presented for normal alkanes and perfluorocarbons. It is shown that by varying the repulsive exponent the range of the potential can be altered, leading to improved predictions of vapor pressures while also reproducing saturated liquid densities to high accuracy. Histogram-reweighting Monte Carlo simulations in the grand canonical ensemble are used to determine the vapor liquid coexistence curves, vapor pressures, heats of vaporization, and critical points for normal alkanes methane through tetradecane, and perfluorocarbons perfluoromethane through perfluorooctane. For all molecules studied, saturated liquid densities are reproduced to within 1% of experiment. Vapor pressures for normal alkanes and perfluorocarbons were predicted to within 3% and 6% of experiment, respectively. Calculations performed for binary mixture vapor-liquid equilibria for propane + pentane show excellent agreement with experiment, while slight deviations are observed for the ethane + perfluoroethane mixture.

  6. Turbulent energy exchange: Calculation and relevance for profile prediction

    SciTech Connect

    Candy, J.

    2013-08-15

    The anomalous heat production due to turbulence is neither routinely calculated in nonlinear gyrokinetic simulations nor routinely retained in profile prediction studies. In this work, we develop a symmetrized method to compute the exchange which dramatically reduces the intermittency in the time-dependent moment, thereby improving the accuracy of the time-average. We also examine the practical impact on transport-timescale simulations, and show that the exchange has only a minor impact on profile evolution for a well-studied DIII-D discharge.

  7. Advancing QCD-based calculations of energy loss

    NASA Astrophysics Data System (ADS)

    Tywoniuk, Konrad

    2013-08-01

    We give a brief overview of the basics and current developments of QCD-based calculations of radiative processes in medium. We put an emphasis on the underlying physics concepts and discuss the theoretical uncertainties inherently associated with the fundamental parameters to be extracted from data. An important area of development is the study of the single-gluon emission in medium. Moreover, establishing the correct physical picture of multi-gluon emissions is imperative for comparison with data. We will report on progress made in both directions and discuss perspectives for the future.

  8. Rotational Energy Transfer of N2 Determined Using a New Ab Initio Potential Energy Surface

    NASA Technical Reports Server (NTRS)

    Huo, Winifred M.; Stallcop, James R.; Partridge, Harry; Langhoff, Stephen R. (Technical Monitor)

    1997-01-01

    A new N2-N2 rigid-rotor surface has been determined using extensive Ab Initio quantum chemistry calculations together with recent experimental data for the second virial coefficient. Rotational energy transfer is studied using the new potential energy surface (PES) employing the close coupling method below 200 cm(exp -1) and coupled state approximation above that. Comparing with a previous calculation based on the PES of van der Avoird et al.,3 it is found that the new PES generally gives larger cross sections for large (delta)J transitions, but for small (delta)J transitions the cross sections are either comparable or smaller. Correlation between the differences in the cross sections and the two PES will be attempted. The computed cross sections will also be compared with available experimental data.

  9. Modeling intermolecular interactions of physisorbed organic molecules using pair potential calculations

    SciTech Connect

    Kroeger, Ingo; Stadtmueller, Benjamin; Wagner, Christian; Weiss, Christian; Temirov, Ruslan; Tautz, F. Stefan; Kumpf, Christian

    2011-12-21

    The understanding and control of epitaxial growth of organic thin films is of crucial importance in order to optimize the performance of future electronic devices. In particular, the start of the submonolayer growth plays an important role since it often determines the structure of the first layer and subsequently of the entire molecular film. We have investigated the structure formation of 3,4,9,10-perylene-tetracarboxylic dianhydride and copper-phthalocyanine molecules on Au(111) using pair-potential calculations based on van der Waals and electrostatic intermolecular interactions. The results are compared with the fundamental lateral structures known from experiment and an excellent agreement was found for these weakly interacting systems. Furthermore, the calculations are even suitable for chemisorptive adsorption as demonstrated for copper-phthalocyanine/Cu(111), if the influence of charge transfer between substrate and molecules is known and the corresponding charge redistribution in the molecules can be estimated. The calculations are of general applicability for molecular adsorbate systems which are dominated by electrostatic and van der Waals interaction.

  10. Sample size calculations for clinical trials targeting tauopathies: A new potential disease target

    PubMed Central

    Whitwell, Jennifer L.; Duffy, Joseph R.; Strand, Edythe A.; Machulda, Mary M.; Tosakulwong, Nirubol; Weigand, Stephen D.; Senjem, Matthew L.; Spychalla, Anthony J.; Gunter, Jeffrey L.; Petersen, Ronald C.; Jack, Clifford R.; Josephs, Keith A.

    2015-01-01

    Disease-modifying therapies are being developed to target tau pathology, and should, therefore, be tested in primary tauopathies. We propose that progressive apraxia of speech should be considered one such target group. In this study, we investigate potential neuroimaging and clinical outcome measures for progressive apraxia of speech and determine sample size estimates for clinical trials. We prospectively recruited 24 patients with progressive apraxia of speech who underwent two serial MRI with an interval of approximately two years. Detailed speech and language assessments included the Apraxia of Speech Rating Scale (ASRS) and Motor Speech Disorders (MSD) severity scale. Rates of ventricular expansion and rates of whole brain, striatal and midbrain atrophy were calculated. Atrophy rates across 38 cortical regions were also calculated and the regions that best differentiated patients from controls were selected. Sample size estimates required to power placebo-controlled treatment trials were calculated. The smallest sample size estimates were obtained with rates of atrophy of the precentral gyrus and supplementary motor area, with both measures requiring less than 50 subjects per arm to detect a 25% treatment effect with 80% power. These measures outperformed the other regional and global MRI measures and the clinical scales. Regional rates of cortical atrophy therefore provide the best outcome measures in progressive apraxia of speech. The small sample size estimates demonstrate feasibility for including progressive apraxia of speech in future clinical treatment trials targeting tau. PMID:26076744

  11. The ozone depletion potentials on halocarbons: Their dependence of calculation assumptions

    NASA Technical Reports Server (NTRS)

    Karol, Igor L.; Kiselev, Andrey A.

    1994-01-01

    The concept of Ozone Depletion Potential (ODP) is widely used in the evaluation of numerous halocarbons and of their replacement effects on ozone, but the methods, assumptions and conditions used in ODP calculations have not been analyzed adequately. In this paper a model study of effects on ozone of the instantaneous releases of various amounts of CH3CCl3 and of CHF2Cl (HCFC-22) for several compositions of the background atmosphere are presented, aimed at understanding connections of ODP values with the assumptions used in their calculations. To facilitate the ODP computation in numerous versions for the long time periods after their releases, the above rather short-lived gases and the one-dimensional radiative photochemical model of the global annually averaged atmospheric layer up to 50 km height are used. The variation of released gas global mass from 1 Mt to 1 Gt leads to ODP value increase with its stabilization close to the upper bound of this range in the contemporary atmosphere. The same variations are analyzed for conditions of the CFC-free atmosphere of 1960's and for the anthropogenically loaded atmosphere in the 21st century according to the known IPCC 'business as usual' scenario. Recommendations for proper ways of ODP calculations are proposed for practically important cases.

  12. A highly accurate ab initio potential energy surface for methane

    NASA Astrophysics Data System (ADS)

    Owens, Alec; Yurchenko, Sergei N.; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter

    2016-09-01

    A new nine-dimensional potential energy surface (PES) for methane has been generated using state-of-the-art ab initio theory. The PES is based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set limit and incorporates a range of higher-level additive energy corrections. These include core-valence electron correlation, higher-order coupled cluster terms beyond perturbative triples, scalar relativistic effects, and the diagonal Born-Oppenheimer correction. Sub-wavenumber accuracy is achieved for the majority of experimentally known vibrational energy levels with the four fundamentals of 12CH4 reproduced with a root-mean-square error of 0.70 cm-1. The computed ab initio equilibrium C-H bond length is in excellent agreement with previous values despite pure rotational energies displaying minor systematic errors as J (rotational excitation) increases. It is shown that these errors can be significantly reduced by adjusting the equilibrium geometry. The PES represents the most accurate ab initio surface to date and will serve as a good starting point for empirical refinement.

  13. A highly accurate ab initio potential energy surface for methane.

    PubMed

    Owens, Alec; Yurchenko, Sergei N; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter

    2016-09-14

    A new nine-dimensional potential energy surface (PES) for methane has been generated using state-of-the-art ab initio theory. The PES is based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set limit and incorporates a range of higher-level additive energy corrections. These include core-valence electron correlation, higher-order coupled cluster terms beyond perturbative triples, scalar relativistic effects, and the diagonal Born-Oppenheimer correction. Sub-wavenumber accuracy is achieved for the majority of experimentally known vibrational energy levels with the four fundamentals of (12)CH4 reproduced with a root-mean-square error of 0.70 cm(-1). The computed ab initio equilibrium C-H bond length is in excellent agreement with previous values despite pure rotational energies displaying minor systematic errors as J (rotational excitation) increases. It is shown that these errors can be significantly reduced by adjusting the equilibrium geometry. The PES represents the most accurate ab initio surface to date and will serve as a good starting point for empirical refinement. PMID:27634258

  14. A highly accurate ab initio potential energy surface for methane.

    PubMed

    Owens, Alec; Yurchenko, Sergei N; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter

    2016-09-14

    A new nine-dimensional potential energy surface (PES) for methane has been generated using state-of-the-art ab initio theory. The PES is based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set limit and incorporates a range of higher-level additive energy corrections. These include core-valence electron correlation, higher-order coupled cluster terms beyond perturbative triples, scalar relativistic effects, and the diagonal Born-Oppenheimer correction. Sub-wavenumber accuracy is achieved for the majority of experimentally known vibrational energy levels with the four fundamentals of (12)CH4 reproduced with a root-mean-square error of 0.70 cm(-1). The computed ab initio equilibrium C-H bond length is in excellent agreement with previous values despite pure rotational energies displaying minor systematic errors as J (rotational excitation) increases. It is shown that these errors can be significantly reduced by adjusting the equilibrium geometry. The PES represents the most accurate ab initio surface to date and will serve as a good starting point for empirical refinement.

  15. Calculated cancer risks for conventional and "potentially reduced exposure product" cigarettes.

    PubMed

    Pankow, James F; Watanabe, Karen H; Toccalino, Patricia L; Luo, Wentai; Austin, Donald F

    2007-03-01

    Toxicant deliveries (by machine smoking) are compiled and associated cancer risks are calculated for 13 carcinogens from 26 brands of conventional cigarettes categorized as "regular" (R), "light" (Lt), or "ultralight" (ULt), and for a reference cigarette. Eight "potentially reduced exposure product" (PREP) cigarettes are also considered. Because agency-to-agency differences exist in the cancer slope factor (CSF) values adopted for some carcinogens, two CSF sets were used in the calculations: set I [U.S. Environmental Protection Agency (EPA)-accepted values plus California EPA-accepted values as needed to fill data gaps] and set II (vice versa). The potential effects of human smoking patterns on cigarette deliveries are considered. Acetaldehyde, 1,3-butadiene, and acrylonitrile are associated with the largest calculated cancer risks for all 26 brands of conventional cigarettes. The calculated risks are proportional to the smoking dose z (pack-years). Using CSF set I and z = 1 pack-year (7,300 cigarettes), the calculated brand-average incremental lifetime cancer risk ILCR(1)(acetaldehyde) values are R, 6 x 10(-5); Lt, 5 x 10(-5); and ULt, 3 x 10(-5) (cf. typical U.S. EPA risk benchmark of 10(-6)). These values are similar, especially given the tendency of smokers to "compensate" when smoking Lt and ULt cigarettes. ILCR(1)(subSigma-lung) is the brand-average per pack-year subtotal risk for the measured human lung carcinogens. Using CSF set I, the ILCR(1)(subSigma-lung) values for R, Lt, and ULt cigarettes account for

  16. Theoretical characterization of the potential energy surface for NH + NO

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    1992-01-01

    The potential energy surface (PES) for NH + NO was characterized using complete active space self-consistent field (CASSCF) gradient calculations to determine the stationary point geometries and frequencies followed by CASSCF/internally contracted configuration interaction (CCI) calculations to refine the energetics. The present results are in qualitative accord with the BAC-MP4 calculations, but there are differences as large as 8 kcal/mol in the detailed energetics. Addition of NH to NO on a (2)A' surface, which correlated with N2 + OH or H + N2O products, involves barriers of 3.2 kcal/mol (trans) and 6.3 kcal/mol (cis). Experimental evidence for these barriers is found in earlier works. The (2)A' surface has no barrier to addition, but does not correlate with products. Surface crossings between the barrierless (2)A' surface and the (2)A' surface may be important. Production of N2 + OH products is predicted to occur via a planar saddle point of (2)A' symmetry. This is in accord with the preferential formation of II(A') lambda doublet levels of OH in earlier experiments. Addition of NH (1)delta to NO is found to occur on an excited state surface and is predicted to lead to N2O product as observed in earlier works.

  17. Multireference configuration interaction calculations of the first six ionization potentials of the uranium atom

    DOE PAGES

    Bross, David H.; Parmar, Payal; Peterson, Kirk A.

    2015-11-12

    The first 6 ionization potentials (IPs) of the uranium atom have been calculated using multireference configuration interaction (MRCI+Q) with extrapolations to the complete basis set (CBS) limit using new all-electron correlation consistent basis sets. The latter were carried out with the third-order Douglas-Kroll-Hess Hamiltonian. Correlation down through the 5s5p5d electrons have been taken into account, as well as contributions to the IPs due to the Lamb shift. Spin-orbit coupling contributions calculated at the 4-component Kramers restricted configuration interaction level, as well as the Gaunt term computed at the Dirac-Hartree-Fock level, were added to the best scalar relativistic results. As amore » result, the final ionization potentials are expected to be accurate to at least 5 kcal/mol (0.2 eV), and thus more reliable than the current experimental values of IP3 through IP6.« less

  18. Multireference configuration interaction calculations of the first six ionization potentials of the uranium atom

    SciTech Connect

    Bross, David H.; Parmar, Payal; Peterson, Kirk A.

    2015-11-12

    The first 6 ionization potentials (IPs) of the uranium atom have been calculated using multireference configuration interaction (MRCI+Q) with extrapolations to the complete basis set (CBS) limit using new all-electron correlation consistent basis sets. The latter were carried out with the third-order Douglas-Kroll-Hess Hamiltonian. Correlation down through the 5s5p5d electrons have been taken into account, as well as contributions to the IPs due to the Lamb shift. Spin-orbit coupling contributions calculated at the 4-component Kramers restricted configuration interaction level, as well as the Gaunt term computed at the Dirac-Hartree-Fock level, were added to the best scalar relativistic results. As a result, the final ionization potentials are expected to be accurate to at least 5 kcal/mol (0.2 eV), and thus more reliable than the current experimental values of IP3 through IP6.

  19. An Accurate Potential Energy Surface for H2O

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Partridge, Harry; Langhoff, Stephen R. (Technical Monitor)

    1997-01-01

    We have carried out extensive high quality ab initio electronic structure calculations of the ground state potential energy surface (PES) and dipole moment function (DMF) for H2O. A small adjustment is made to the PES to improve the agreement of line positions from theory and experiment. The theoretical line positions are obtained from variational ro-vibrational calculations using the exact kinetic energy operator. For the lines being fitted, the root-mean-square error was reduced from 6.9 to 0.08 /cm. We were then able to match 30,092 of the 30,117 lines from the HITRAN 96 data base to theoretical lines, and 80% of the line positions differed less than 0.1 /cm. About 3% of the line positions in the experimental data base appear to be incorrect. Theory predicts the existence of many additional weak lines with intensities above the cutoff used in the data base. To obtain results of similar accuracy for HDO, a mass dependent correction to the PH is introduced and is parameterized by simultaneously fitting line positions for HDO and D2O. The mass dependent PH has good predictive value for T2O and HTO. Nonadiabatic effects are not explicitly included. Line strengths for vibrational bands summed over rotational levels usually agree well between theory and experiment, but individual line strengths can differ greatly. A high temperature line list containing about 380 million lines has been generated using the present PES and DMF

  20. Tunable redox potential of nonmetal doped monolayer MoS2: First principle calculations

    NASA Astrophysics Data System (ADS)

    Lu, S.; Li, C.; Zhao, Y. F.; Gong, Y. Y.; Niu, L. Y.; Liu, X. J.

    2016-10-01

    Doping is an effective method to alter the electronic behavior of materials by forming new chemical bonds and bringing bond relaxation. With this aid of first principle calculations, the crystal configuration and electronic properties of monolayer MoS2 have been modulated by the nonmetal (NM) dopants (H, B, C, N, O, F, Si, P, Cl, As, Se, Br, Te and I), and the thermodynamic stability depending on the preparation conditions (Mo-rich and S-rich conditions) were discussed. Results shown that, the NM dopants substituted preferentially for S under Mo-rich condition, the electronic distribution around the dopants and the nearby Mo atoms are changed by the new formed Mo-NM bonds and bands relaxation. Compared to pristine monolayer MoS2, the NM ions with odd chemical valences enhance the oxidation potential and reduce the reduction potential of specimens, but the NM ions with even chemical valences have the opposite effects on the redox potentials. Compared to the NM ions with even chemical valences, the lone pair electrons in NM ions with odd chemical valences can extra interact with the Mo ions and reduces the ECBM and EVBM values of specimens. It offers a simple way to design various monolayer MoS2 based catalysts in order to catalyze different materials by chose the reasonable dopants for stronger oxidation or reduction potential.

  1. The Suppression of Energy Discretization Errors in Multigroup Transport Calculations

    SciTech Connect

    Larsen, Edward

    2013-06-17

    The Objective of this project is to develop, implement, and test new deterministric methods to solve, as efficiently as possible, multigroup neutron transport problems having an extremely large number of groups. Our approach was to (i) use the standard CMFD method to "coarsen" the space-angle grid, yielding a multigroup diffusion equation, and (ii) use a new multigrid-in-space-and-energy technique to efficiently solve the multigroup diffusion problem. The overall strategy of (i) how to coarsen the spatial an energy grids, and (ii) how to navigate through the various grids, has the goal of minimizing the overall computational effort. This approach yields not only the fine-grid solution, but also coarse-group flux-weighted cross sections that can be used for other related problems.

  2. Absolute surface energy calculations of Wurtzite (0001)/(000-1): a study of ZnO and GaN

    NASA Astrophysics Data System (ADS)

    Zhang, Jingzhao; Zhang, Yiou; Tse, Kinfai; Deng, Bei; Xu, Hu; Zhu, Junyi

    The accurate absolute surface energies of (0001)/(000-1) surfaces of wurtzite structures are crucial in determining the thin film growth mode of important energy materials. However, the surface energies still remain to be solved due to the intrinsic difficulty of calculating dangling bond energy of asymmetrically bonded surface atoms. We used a pseudo-hydrogen passivation method to estimate the dangling bond energy and calculate the polar surfaces of ZnO and GaN. The calculations were based on the pseudo chemical potentials obtained from a set of tetrahedral clusters or simple pseudo-molecules, using density functional theory approaches, for both GGA and HSE. And the surface energies of (0001)/(000-1) surfaces of wurtzite ZnO and GaN we obtained showed relatively high self-consistencies. A wedge structure calculation with a new bottom surface passivation scheme of group I and group VII elements was also proposed and performed to show converged absolute surface energy of wurtzite ZnO polar surfaces. Part of the computing resources was provided by the High Performance Cluster Computing Centre, Hong Kong Baptist University. This work was supported by the start-up funding and direct Grant with the Project code of 4053134 at CUHK.

  3. Computational efficiences for calculating rare earth f^n energies

    NASA Astrophysics Data System (ADS)

    Beck, Donald R.

    2009-05-01

    RecentlyootnotetextD. R. Beck and E. J. Domeier, Can. J. Phys. Walter Johnson issue, Jan. 2009., we have used new computational strategies to obtain wavefunctions and energies for Gd IV 4f^7 and 4f^65d levels. Here we extend one of these techniques to allow efficent inclusion of 4f^2 pair correlation effects using radial pair energies obtained from much simpler calculationsootnotetexte.g. K. Jankowski et al., Int. J. Quant. Chem. XXVII, 665 (1985). and angular factors which can be simply computedootnotetextD. R. Beck and C. A. Nicolaides, Excited States in Quantum Chemistry, C. A. Nicolaides and D. R. Beck (editors), D. Reidel (1978), p. 105ff.. This is a re-vitalization of an older ideaootnotetextI. Oksuz and O. Sinanoglu, Phys. Rev. 181, 54 (1969).. We display relationships between angular factors involving the exchange of holes and electrons (e.g. f^6 vs f^8, f^13d vs fd^9). We apply the results to Tb IV and Gd IV, whose spectra is largely unknown, but which may play a role in MRI medicine as endohedral metallofullerenes (e.g. Gd3N-C80ootnotetextM. C. Qian and S. N. Khanna, J. Appl. Phys. 101, 09E105 (2007).). Pr III results are in good agreement (910 cm-1) with experiment. Pu I 5f^2 radial pair energies are also presented.

  4. Perturbative Calculation of Quasi-Potential in Non-equilibrium Diffusions: A Mean-Field Example

    NASA Astrophysics Data System (ADS)

    Bouchet, Freddy; Gawȩdzki, Krzysztof; Nardini, Cesare

    2016-06-01

    In stochastic systems with weak noise, the logarithm of the stationary distribution becomes proportional to a large deviation rate function called the quasi-potential. The quasi-potential, and its characterization through a variational problem, lies at the core of the Freidlin-Wentzell large deviations theory (Freidlin and Wentzell, Random perturbations of dynamical systems, 2012). In many interacting particle systems, the particle density is described by fluctuating hydrodynamics governed by Macroscopic Fluctuation Theory (Bertini et al., arXiv:1404.6466 , 2014), which formally fits within Freidlin-Wentzell's framework with a weak noise proportional to 1/√{N}, where N is the number of particles. The quasi-potential then appears as a natural generalization of the equilibrium free energy to non-equilibrium particle systems. A key physical and practical issue is to actually compute quasi-potentials from their variational characterization for non-equilibrium systems for which detailed balance does not hold. We discuss how to perform such a computation perturbatively in an external parameter λ , starting from a known quasi-potential for λ =0. In a general setup, explicit iterative formulae for all terms of the power-series expansion of the quasi-potential are given for the first time. The key point is a proof of solvability conditions that assure the existence of the perturbation expansion to all orders. We apply the perturbative approach to diffusive particles interacting through a mean-field potential. For such systems, the variational characterization of the quasi-potential was proven by Dawson and Gartner (Stochastics 20:247-308, 1987; Stochastic differential systems, vol 96, pp 1-10, 1987). Our perturbative analysis provides new explicit results about the quasi-potential and about fluctuations of one-particle observables in a simple example

  5. Computed potential energy surfaces for chemical reactions

    NASA Technical Reports Server (NTRS)

    Heinemann, K.; Walch, Stephen P.

    1992-01-01

    The work on the NH + NO system which was described in the last progress report was written up and a draft of the manuscript is included in the appendix. The appendix also contains a draft of a manuscript on an Ar + H + H surface. New work which was completed in the last six months includes the following: (1) calculations on the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels in the CH3 + OH reaction; (2) calculations for the NH2 + O reaction; (3) calculations for the CH3 + O2 reaction; and (4) calculations for CH3O and the two decomposition channels--CH2OH and H + H2CO. Detailed descriptions of this work will be given in manuscripts; however, brief descriptions of the CH3 + OH and CH3 + O2 projects are given.

  6. Anharmonic Rovibrational Calculations of Singlet Cyclic C4 Using a New Ab Initio Potential and a Quartic Force

    NASA Technical Reports Server (NTRS)

    Wang, Xiaohong; Huang, Xinchuan; Bowman, Joel M.; Lee, Timothy J.

    2013-01-01

    We report a CCSD(T)/cc-pCV5Z quartic force field (QFF) and a semi-global CCSD(T)-F12b/aug-cc-pVTZ potential energy surface (PES) for singlet, cyclic C4. Vibrational fundamentals, combinations and overtones are obtained using vibrational second-order perturbation theory (VPT2) and the vibrational configurationinteraction (VCI) approach. Agreement is within 10 cm(exp -1) between the VCI calculated fundamentals on the QFF and PES using the MULTIMODE (MM) program, and VPT2 and VCI results agree for the fundamentals. The agreement between VPT2- QFF and MM-QFF results is also good for the C4 combinations and overtones. The J = 1 and J = 2 rovibrational energies are reported from both VCI (MM) on the PES and VPT2 on the QFF calculations. The spectroscopic constants of (12)C4 and two C(sub 2v)-symmetry, single (13)C-substituted isotopologues are presented, which may help identification of cyclic C4 in future experimental analyses or astronomical observations.

  7. Anharmonic rovibrational calculations of singlet cyclic C4 using a new ab initio potential and a quartic force field.

    PubMed

    Wang, Xiaohong; Huang, Xinchuan; Bowman, Joel M; Lee, Timothy J

    2013-12-14

    We report a CCSD(T)/cc-pCV5Z quartic force field (QFF) and a semi-global CCSD(T)-F12b/aug-cc-pVTZ potential energy surface (PES) for singlet, cyclic C4. Vibrational fundamentals, combinations, and overtones are obtained using vibrational second-order perturbation theory (VPT2) and the vibrational configuration-interaction (VCI) approach. Agreement is within 10 cm(-1) between the VCI calculated fundamentals on the QFF and PES using the MULTIMODE (MM) program, and VPT2 and VCI results agree for the fundamentals. The agreement between VPT2-QFF and MM-QFF results is also good for the C4 combinations and overtones. The J = 1 and J = 2 rovibrational energies are reported from both VCI (MM) on the PES and VPT2 on the QFF calculations. The spectroscopic constants of (12)C4 and two C2v-symmetry, single (13)C-substituted isotopologues are presented, which may help identification of cyclic C4 in future experimental analyses or astronomical observations. PMID:24329063

  8. Calculation of the thermoneutral potential of NiCd and NiH2 cells

    NASA Technical Reports Server (NTRS)

    Zimmerman, Albert H.

    1994-01-01

    The thermoneutral potential of a nickel cadmium or nickel hydrogen cell is the potential at which the cell charge or discharge process puts out zero heat, and thus is the potential corresponding to the enthalpy change of the charge/discharge reaction, delta H. A relatively straightforward method for obtaining the thermoneutral potential E(sub tn), is based on the measured potential and temperature derivative of the cell reactions, which are related to the free energy change delta G, and entropy change delta S, respectively. Particularly in the nickel hydrogen cell, the pressure of hydrogen can often vary over an order of magnitude or more during the course of a charge or discharge. In a nickel cadmium cell, although significant changes in oxygen pressure can occur during charge or discharge, since oxygen does not enter into the charge/discharge reaction, these pressure changes are related to the heat generated from oxygen evolution and recombination. However, the entropy changes due to changes in hydrogen pressure relative to the 1 atm standard state must be included to apply this method to the nickel hydrogen cell.

  9. Calculations of energy levels and lifetimes of low-lying states of barium and radium

    SciTech Connect

    Dzuba, V. A.; Ginges, J. S. M.

    2006-03-15

    We use the configuration-interaction method and many-body perturbation theory to perform accurate calculations of energy levels, transition amplitudes, and lifetimes of low-lying states of barium and radium. Calculations for radium are needed for the planning of measurements of parity- and time-invariance-violating effects which are strongly enhanced in this atom. Calculations for barium are used to control the accuracy of the calculations.

  10. Ground- and excited-state properties of inorganic solids from full-potential density-functional calculations

    NASA Astrophysics Data System (ADS)

    Ravindran, P.; Vidya, R.; Vajeeston, P.; Kjekshus, A.; Fjellvåg, H.

    2003-12-01

    The development in theoretical condensed-matter science based on density-functional theory (DFT) has reached a level where it is possible, from "parameter-free" quantum mechanical calculations to obtain total energies, forces, vibrational frequencies, magnetic moments, mechanical and optical properties and so forth. The calculation of such properties are important in the analyses of experimental data and they can be predicted with a precision that is sufficient for comparison with experiments. It is almost impossible to do justice to all developments achieved by DFT because of its rapid growth. Hence, it has here been focused on a few advances, primarily from our laboratory. Unusual bonding behaviors in complex materials are conveniently explored using the combination of charge density, charge transfer, and electron-localization function along with crystal-orbital Hamilton-population analyses. It is indicated that the elastic properties of materials can reliably be predicted from DFT calculations if one takes into account the structural relaxations along with gradient corrections in the calculations. Experimental techniques have their limitations in studies of the structural stability and pressure-induced structural transitions in hydride materials whereas the present theoretical approach can be applied to reliably predict properties under extreme pressures. From the spin-polarized, relativistic full-potential calculations one can study novel materials such as ruthenates, quasi-one-dimensional oxides, and spin-, charge-, and orbital-ordering in magnetic perovskite-like oxides. The importance of orbital-polarization correction to the DFT to predict the magnetic anisotropy in transition-metal compounds and magnetic moments in lanthanides and actinides are emphasized. Apart from the full-potential treatment, proper magnetic ordering as well as structural distortions have to be taken into account to predict correctly the insulating behavior of transition-metal oxides

  11. Hybrid MP2/MP4 potential surfaces in VSCF calculations of IR spectra: applications for organic molecules.

    PubMed

    Knaanie, Roie; Šebek, Jiří; Kalinowski, Jaroslaw; Benny Gerber, R

    2014-02-01

    This study introduces an improved hybrid MP2/MP4 ab initio potential for vibrational spectroscopy calculations which is very accurate, yet without high computational demands. The method uses harmonic vibrational calculations with the MP4(SDQ) potential to construct an improved MP2 potential by coordinate scaling. This improved MP2 potential is used for the anharmonic VSCF calculation. The method was tested spectroscopically for four molecules: butane, acetone, ethylene and glycine. Very good agreement with experiment was found. For most of the systems, the more accurate harmonic treatment considerably improved the MP2 anharmonic results. PMID:23838574

  12. New potential energy surface for the HCS(+)-He system and inelastic rate coefficients.

    PubMed

    Dubernet, Marie-Lise; Quintas-Sánchez, Ernesto; Tuckey, Philip

    2015-07-28

    A new high quality potential energy surface is calculated at a coupled-cluster single double triple level with an aug-cc-pV5Z basis set for the HCS(+)-He system. This potential energy surface is used in low energy quantum scattering calculations to provide a set of (de)-excitation cross sections and rate coefficients among the first 20 rotational levels of HCS(+) by He in the range of temperature from 5 K to 100 K. The paper discusses the impact of the new ab initio potential energy surface on the cross sections at low energy and provides a comparison with the HCO(+)-He system. The HCS(+)-He rate coefficients for the strongest transitions differ by factors of up to 2.5 from previous rate coefficients; thus, analysis of astrophysical spectra should be reconsidered with the new rate coefficients.

  13. Free-energy calculation methods for collective phenomena in membranes

    NASA Astrophysics Data System (ADS)

    Smirnova, Yuliya G.; Fuhrmans, Marc; Barragan Vidal, Israel A.; Müller, Marcus

    2015-09-01

    Collective phenomena in membranes are those which involve the co-operative reorganization of many molecules. Examples of these are membrane fusion, pore formation, bending, adhesion or fission. The time and length scales, on which these processes occur, pose a challenge for atomistic simulations. Therefore, in order to solve the length scale problem it is popular to introduce a coarse-grained representation. To facilitate sampling of the relevant states additional computational techniques, which encourage the system to explore the free-energy landscape far from equilibrium and visit transition states, are needed. These computational techniques provide insights about the free-energy changes involved in collective transformations of membranes, yielding information about the rate limiting states, the transformation mechanism and the influence of architectural, compositional and interaction parameters. A common approach is to identify an order parameter (or reaction coordinate), which characterizes the pathway of membrane reorganization. However, no general strategy exists to define such an order parameter that can properly describe cooperative reorganizations in membranes. Recently developed methods can overcome this problem of the order-parameter choice and allow us to study collective phenomena in membranes. We will discuss such methods as thermodynamic integration, umbrella sampling, and the string method and results provided by their applications to particle-based simulations, particularly focusing on membrane fusion and pore formation.

  14. Parallel implementation of electronic structure energy, gradient, and Hessian calculations.

    PubMed

    Lotrich, V; Flocke, N; Ponton, M; Yau, A D; Perera, A; Deumens, E; Bartlett, R J

    2008-05-21

    ACES III is a newly written program in which the computationally demanding components of the computational chemistry code ACES II [J. F. Stanton et al., Int. J. Quantum Chem. 526, 879 (1992); [ACES II program system, University of Florida, 1994] have been redesigned and implemented in parallel. The high-level algorithms include Hartree-Fock (HF) self-consistent field (SCF), second-order many-body perturbation theory [MBPT(2)] energy, gradient, and Hessian, and coupled cluster singles, doubles, and perturbative triples [CCSD(T)] energy and gradient. For SCF, MBPT(2), and CCSD(T), both restricted HF and unrestricted HF reference wave functions are available. For MBPT(2) gradients and Hessians, a restricted open-shell HF reference is also supported. The methods are programed in a special language designed for the parallelization project. The language is called super instruction assembly language (SIAL). The design uses an extreme form of object-oriented programing. All compute intensive operations, such as tensor contractions and diagonalizations, all communication operations, and all input-output operations are handled by a parallel program written in C and FORTRAN 77. This parallel program, called the super instruction processor (SIP), interprets and executes the SIAL program. By separating the algorithmic complexity (in SIAL) from the complexities of execution on computer hardware (in SIP), a software system is created that allows for very effective optimization and tuning on different hardware architectures with quite manageable effort. PMID:18500853

  15. Calculation of resonance energy transfer in crowded biological membranes.

    PubMed

    Zimet, D B; Thevenin, B J; Verkman, A S; Shohet, S B; Abney, J R

    1995-04-01

    Analytical and numerical models were developed to describe fluorescence resonance energy transfer (RET) in crowded biological membranes. It was assumed that fluorescent donors were linked to membrane proteins and that acceptors were linked to membrane lipids. No restrictions were placed on the location of the donor within the protein or the partitioning of acceptors between the two leaflets of the bilayer; however, acceptors were excluded from the area occupied by proteins. Analytical equations were derived that give the average quantum yield of a donor at low protein concentrations. Monte Carlo simulations were used to generate protein and lipid distributions that were linked numerically with RET equations to determine the average quantum yield and the distribution of donor fluorescence lifetimes at high protein concentrations, up to 50% area fraction. The Monte Carlo results show such crowding always reduces the quantum yield, probably because crowding increases acceptor concentrations near donor-bearing proteins; the magnitude of the reduction increases monotonically with protein concentration. The Monte Carlo results also show that the distribution of fluorescence lifetimes can differ markedly, even for systems possessing the same average lifetime. The dependence of energy transfer on acceptor concentration, protein radius, donor position within the protein, and the fraction of acceptors in each leaflet was also examined. The model and results are directly applicable to the analysis of RET data obtained from biological membranes; their application should result in a more complete and accurate determination of the structures of membrane components. PMID:7787045

  16. Parallel implementation of electronic structure energy, gradient, and Hessian calculations

    NASA Astrophysics Data System (ADS)

    Lotrich, V.; Flocke, N.; Ponton, M.; Yau, A. D.; Perera, A.; Deumens, E.; Bartlett, R. J.

    2008-05-01

    ACES III is a newly written program in which the computationally demanding components of the computational chemistry code ACES II [J. F. Stanton et al., Int. J. Quantum Chem. 526, 879 (1992); [ACES II program system, University of Florida, 1994] have been redesigned and implemented in parallel. The high-level algorithms include Hartree-Fock (HF) self-consistent field (SCF), second-order many-body perturbation theory [MBPT(2)] energy, gradient, and Hessian, and coupled cluster singles, doubles, and perturbative triples [CCSD(T)] energy and gradient. For SCF, MBPT(2), and CCSD(T), both restricted HF and unrestricted HF reference wave functions are available. For MBPT(2) gradients and Hessians, a restricted open-shell HF reference is also supported. The methods are programed in a special language designed for the parallelization project. The language is called super instruction assembly language (SIAL). The design uses an extreme form of object-oriented programing. All compute intensive operations, such as tensor contractions and diagonalizations, all communication operations, and all input-output operations are handled by a parallel program written in C and FORTRAN 77. This parallel program, called the super instruction processor (SIP), interprets and executes the SIAL program. By separating the algorithmic complexity (in SIAL) from the complexities of execution on computer hardware (in SIP), a software system is created that allows for very effective optimization and tuning on different hardware architectures with quite manageable effort.

  17. Improved DFT Potential Energy Surfaces via Improved Densities.

    PubMed

    Kim, Min-Cheol; Park, Hansol; Son, Suyeon; Sim, Eunji; Burke, Kieron

    2015-10-01

    Density-corrected DFT is a method that cures several failures of self-consistent semilocal DFT calculations by using a more accurate density instead. A novel procedure employs the Hartree-Fock density to bonds that are more severely stretched than ever before. This substantially increases the range of accurate potential energy surfaces obtainable from semilocal DFT for many heteronuclear molecules. We show that this works for both neutral and charged molecules. We explain why and explore more difficult cases, for example, CH(+), where density-corrected DFT results are even better than sophisticated methods like CCSD. We give a simple criterion for when DC-DFT should be more accurate than self-consistent DFT that can be applied for most cases. PMID:26722874

  18. Calculation of Steady-state Evaporation for an Arbitrary Matrix Potential at Ground Surface

    NASA Astrophysics Data System (ADS)

    Liu, X.; Zhan, H.

    2014-12-01

    The water loss from soil by evaporation and the amount of ground water available to plants due to the upward movement of water from a water table is an important topic in many disciplines such as soil science, hydrology, and plant physiology. Although water evaporation in actual field setting is a highly complex process, a nearly steady upward flow from a water table to a bare soil surface may be established if the daily evaporative demand is reasonably uniform for a long period of time. While the maximum potential rate of evaporation from the ground surface depends on atmospheric conditions, the actual flux across the soil surface is limited by the ability of the porous medium for transmitting water from the unsaturated zone.The purpose of this study is to calculate the steady-state evaporation for an arbitrary matrix potential at bare soil surface above a shallow water table, while the unsaturated hydraulic conductivity is a nonlinear function of water content or matrix potential. The Haverkamp function and the Brooks-Corey function for the unsaturated hydraulic conductivity are used, and the study results are contrast among the solution developed from the two retention equation and HYDRUS simulation.

  19. Methods for finding transition states on reduced potential energy surfaces

    NASA Astrophysics Data System (ADS)

    Burger, Steven K.; Ayers, Paul W.

    2010-06-01

    Three new algorithms are presented for determining transition state (TS) structures on the reduced potential energy surface, that is, for problems in which a few important degrees of freedom can be isolated. All three methods use constrained optimization to rapidly find the TS without an initial Hessian evaluation. The algorithms highlight how efficiently the TS can be located on a reduced surface, where the rest of the degrees of freedom are minimized. The first method uses a nonpositive definite quasi-Newton update for the reduced degrees of freedom. The second uses Shepard interpolation to fit the Hessian and starts from a set of points that bound the TS. The third directly uses a finite difference scheme to calculate the reduced degrees of freedom of the Hessian of the entire system, and searches for the TS on the full potential energy surface. All three methods are tested on an epoxide hydrolase cluster, and the ring formations of cyclohexane and cyclobutenone. The results indicate that all the methods are able to converge quite rapidly to the correct TS, but that the finite difference approach is the most efficient.

  20. Pre- and post- scission particle emission in 3D Langevin calculations with various macroscopic potentials

    NASA Astrophysics Data System (ADS)

    Mazurek, K.; Nadtochy, P. N.; Schmitt, C.; Wasiak, P.; Kmiecik, M.; Maj, A.; Bonnet, E.; Chbihi, A.; Frankland, J.; Gruyer, D.; Wieleczko, J.-P.

    2013-12-01

    The fission dynamics described by solving differential equations of the Langevin type in three dimensional space of the deformation parameters is very sensitive on the choice of the macroscopic components such as potential energy models. The mass or charge distribution or total kinetic energy has been already shown to be different when one uses the Finite Range Liquid Drop Model or Lublin - Strasbourg Drop model. Also the shape-dependent congruence or shape-dependent Wigner energy and A0 terms are important especially for the fission of medium mass nuclei. We would like to make step forward and answer the question about the varying of the post-scission multiplicity by including different PES. Up to now there are only few experimental data for the medium mass nuclei where the pre- and post- scission emission has been estimated and isotopic distributions have been shown. The isotopic distributions of the fission products for light compound nucleus such as 111 In with two beam energies (Ebeam = 10.6 AMeV and 5.9 AMeV) and two heavy systems: 229Np with Ebeam = 7.4 AMeV and 260 No (Ebeam = 6 AMeV and 7.5 AMeV) have been studied theoretically. The agreement with the experimental data is discussed.

  1. Recent advances in electronic structure theory and their influence on the accuracy of ab initio potential energy surfaces

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Taylor, Peter R.

    1989-01-01

    Recent advances in electronic structure theory and the availability of high speed vector processors have substantially increased the accuracy of ab initio potential energy surfaces. The recently developed atomic natural orbital approach for basis set contraction has reduced both the basis set incompleteness and superposition errors in molecular calculations. Furthermore, full CI calculations can often be used to calibrate a CASSCF/MRCI approach that quantitatively accounts for the valence correlation energy. These computational advances also provide a vehicle for systematically improving the calculations and for estimating the residual error in the calculations. Calculations on selected diatomic and triatomic systems will be used to illustrate the accuracy that currently can be achieved for molecular systems. In particular, the F + H2 yields HF + H potential energy hypersurface is used to illustrate the impact of these computational advances on the calculation of potential energy surfaces.

  2. Recent advances in electronic structure theory and their influence on the accuracy of ab initio potential energy surfaces

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Taylor, Peter R.

    1988-01-01

    Recent advances in electronic structure theory and the availability of high speed vector processors have substantially increased the accuracy of ab initio potential energy surfaces. The recently developed atomic natural orbital approach for basis set contraction has reduced both the basis set incompleteness and superposition errors in molecular calculations. Furthermore, full CI calculations can often be used to calibrate a CASSCF/MRCI approach that quantitatively accounts for the valence correlation energy. These computational advances also provide a vehicle for systematically improving the calculations and for estimating the residual error in the calculations. Calculations on selected diatomic and triatomic systems will be used to illustrate the accuracy that currently can be achieved for molecular systems. In particular, the F+H2 yields HF+H potential energy hypersurface is used to illustrate the impact of these computational advances on the calculation of potential energy surfaces.

  3. Second-Order Perturbation Theory for Fractional Occupation Systems: Applications to Ionization Potential and Electron Affinity Calculations.

    PubMed

    Su, Neil Qiang; Xu, Xin

    2016-05-10

    Recently, we have developed an integration approach for the calculations of ionization potentials (IPs) and electron affinities (EAs) of molecular systems at the level of second-order Møller-Plesset (MP2) (Su, N. Q.; Xu, X. J. Chem. Theory Comput. 11, 4677, 2015), where the full MP2 energy gradient with respect to the orbital occupation numbers was derived but only at integer occupations. The theory is completed here to cover the fractional occupation systems, such that Slater's transition state concept can be used to have accurate predictions of IPs and EAs. Antisymmetrized Goldstone diagrams have been employed for interpretations and better understanding of the derived equations, where two additional rules were introduced in the present work specifically for hole or particle lines with fractional occupation numbers.

  4. ATOMIC AND MOLECULAR PHYSICS: Model Potential Calculations of Oscillator Strength Spectra of Rydberg Li Atoms in External Fields

    NASA Astrophysics Data System (ADS)

    Meng, Hui-Yan; Shi, Ting-Yun

    2009-08-01

    By combining the B-spline basis set with model potential (B-spline + MP), we present oscillator strength spectra of Rydberg Li atoms in external fields. The photoabsorption spectra are analyzed. Over the narrow energy ranges considered in this paper, the structure of the spectra can be independent of the initial state chosen for a given atom. Our results are in good agreement with previous high-precision experimental data and theoretical calculations, where the R-matrix approach together with multichannel quantum defect theory (R-matrix+MQDT) was used. It is suggested that the present methods can be applied to deal with the oscillator strength spectra of Rydberg atoms in crossed electric and magnetic fields.

  5. Second-Order Perturbation Theory for Fractional Occupation Systems: Applications to Ionization Potential and Electron Affinity Calculations.

    PubMed

    Su, Neil Qiang; Xu, Xin

    2016-05-10

    Recently, we have developed an integration approach for the calculations of ionization potentials (IPs) and electron affinities (EAs) of molecular systems at the level of second-order Møller-Plesset (MP2) (Su, N. Q.; Xu, X. J. Chem. Theory Comput. 11, 4677, 2015), where the full MP2 energy gradient with respect to the orbital occupation numbers was derived but only at integer occupations. The theory is completed here to cover the fractional occupation systems, such that Slater's transition state concept can be used to have accurate predictions of IPs and EAs. Antisymmetrized Goldstone diagrams have been employed for interpretations and better understanding of the derived equations, where two additional rules were introduced in the present work specifically for hole or particle lines with fractional occupation numbers. PMID:27010405

  6. Constrained Broyden Dimer Method with Bias Potential for Exploring Potential Energy Surface of Multistep Reaction Process.

    PubMed

    Shang, Cheng; Liu, Zhi-Pan

    2012-07-10

    To predict the chemical activity of new matter is an ultimate goal in chemistry. The identification of reaction pathways using modern quantum mechanics calculations, however, often requires a high demand in computational power and good chemical intuition on the reaction. Here, a new reaction path searching method is developed by combining our recently developed transition state (TS) location method, namely, the constrained Broyden dimer method, with a basin-filling method via bias potentials, which allows the system to walk out from the energy traps at a given reaction direction. In the new method, the reaction path searching starts from an initial state without the need for preguessing the TS-like or final state structure and can proceed iteratively to the final state by locating all related TSs and intermediates. In each elementary reaction step, a reaction direction, such as a bond breaking, needs to be specified, the information of which is refined and preserved as a normal mode through biased dimer rotation. The method is tested successfully on the Baker reaction system (50 elementary reactions) with good efficiency and stability and is also applied to the potential energy surface exploration of multistep reaction processes in the gas phase and on the surface. The new method can be applied for the computational screening of new catalytic materials with a minimum requirement of chemical intuition.

  7. Calculations of the IR spectra of bend fundamentals of (H2O)n=3,4,5 using the WHBB_2 potential and dipole moment surfaces.

    PubMed

    Wang, Yimin; Bowman, Joel M

    2016-09-14

    Stimulated by new experiments from the Havenith group, we report IR spectra of the bend fundamentals of (H2O)n=3,4,5, using anharmonic, coupled-mode VSCF/VCI calculations, done in a subspace of modes consisting of all the monomer bends plus the hydrogen-bonded OH stretches. Double-harmonic spectra are also reported. All calculations employ a faster version of the ab initio WHBB potential and also a more accurate representation of the dipole moment surface, reported previously. Comparisons at the harmonic level are made with previous high-level ab initio calculations, notably those of Howard and Tschumper and also with harmonic frequencies from the semi-empirical TTM3-F potential, which have been reported previously by Howard and Tschumper. The calculations provide energies and intensities of the hydrogen-bonded OH stretches and these are also presented and briefly discussed. PMID:27523256

  8. Application of potential constants: Empirical determination of molecular energy components for diatomic molecules—II

    NASA Astrophysics Data System (ADS)

    Ohwada, Ken

    The harmonic and anharmonic potential (force) constants which are usually available from a normal coordinate analysis for a diatomic molecule are applied to determine the molecular energy components such as the electronic kinetic energy, the total electrostatic potential energy, the electron—nuclear attraction energy, the electron—electron repulsion energy, the nuclear—nuclear repulsion energy, and the Hartree—Fock eigen-value sum. The method developed here is based on an inhomogeneous linear third-order differential equation derived from the quantum mechanical virial theorem, and a homogeneity hypothesis of the molecular energy with respect to the atomic number. To confirm the utility of the method, the calculated molecular energy components of diatomic molecules are compared with available Hartree—Fock data. It is concluded from this data that the present method is simple and useful for evaluating the molecular energy components of various diatomic molecules.

  9. Properties of metastable alkaline-earth-metal atoms calculated using an accurate effective core potential

    SciTech Connect

    Santra, Robin; Christ, Kevin V.; Greene, Chris H.

    2004-04-01

    The first three electronically excited states in the alkaline-earth-metal atoms magnesium, calcium, and strontium comprise the (nsnp){sup 3}P{sub J}{sup o}(J=0,1,2) fine-structure manifold. All three states are metastable and are of interest for optical atomic clocks as well as for cold-collision physics. An efficient technique--based on a physically motivated potential that models the presence of the ionic core--is employed to solve the Schroedinger equation for the two-electron valence shell. In this way, radiative lifetimes, laser-induced clock shifts, and long-range interaction parameters are calculated for metastable Mg, Ca, and Sr.

  10. Calculating event-triggered average synaptic conductances from the membrane potential.

    PubMed

    Pospischil, Martin; Piwkowska, Zuzanna; Rudolph, Michelle; Bal, Thierry; Destexhe, Alain

    2007-03-01

    The optimal patterns of synaptic conductances for spike generation in central neurons is a subject of considerable interest. Ideally such conductance time courses should be extracted from membrane potential (V(m)) activity, but this is difficult because the nonlinear contribution of conductances to the V(m) renders their estimation from the membrane equation extremely sensitive. We outline here a solution to this problem based on a discretization of the time axis. This procedure can extract the time course of excitatory and inhibitory conductances solely from the analysis of V(m) activity. We test this method by calculating spike-triggered averages of synaptic conductances using numerical simulations of the integrate-and-fire model subject to colored conductance noise. The procedure was also tested successfully in biological cortical neurons using conductance noise injected with dynamic clamp. This method should allow the extraction of synaptic conductances from V(m) recordings in vivo.

  11. Transonic flow analysis for rotors. Part 2: Three-dimensional, unsteady, full-potential calculation

    NASA Technical Reports Server (NTRS)

    Chang, I. C.

    1985-01-01

    A numerical method is presented for calculating the three-dimensional unsteady, transonic flow past a helicopter rotor blade of arbitrary geometry. The method solves the full-potential equations in a blade-fixed frame of reference by a time-marching implicit scheme. At the far-field, a set of first-order radiation conditions is imposed, thus minimizing the reflection of outgoing wavelets from computational boundaries. Computed results are presented to highlight radial flow effects in three dimensions, to compare surface pressure distributions to quasi-steady predictions, and to predict the flow field on a swept-tip blade. The results agree well with experimental data for both straight- and swept-tip blade geometries.

  12. Energy in America: Progress and Potential.

    ERIC Educational Resources Information Center

    American Petroleum Inst., Washington, DC.

    An overview of America's energy situation is presented with emphasis on recent progress, the risk of depending upon foreign oil, and policy choices. Section one reviews the energy problems of the 1970s, issues of the 1980s, concerns for the future, and choices that if made today could alleviate future problems. Section two examines past problems,…

  13. Energy conservation potential of surface modification technologies

    SciTech Connect

    Le, H.K.; Horne, D.M.; Silberglitt, R.S.

    1985-09-01

    This report assesses the energy conservation impact of surface modification technologies on the metalworking industries. The energy conservation impact of surface modification technologies on the metalworking industries is assessed by estimating their friction and wear tribological sinks and the subsequent reduction in these sinks when surface modified tools are used. Ion implantation, coatings, and laser and electron beam surface modifications are considered.

  14. The Potential Energy of an Autoencoder.

    PubMed

    Kamyshanska, Hanna; Memisevic, Roland

    2015-06-01

    Autoencoders are popular feature learning models, that are conceptually simple, easy to train and allow for efficient inference. Recent work has shown how certain autoencoders can be associated with an energy landscape, akin to negative log-probability in a probabilistic model, which measures how well the autoencoder can represent regions in the input space. The energy landscape has been commonly inferred heuristically, by using a training criterion that relates the autoencoder to a probabilistic model such as a Restricted Boltzmann Machine (RBM). In this paper we show how most common autoencoders are naturally associated with an energy function, independent of the training procedure, and that the energy landscape can be inferred analytically by integrating the reconstruction function of the autoencoder. For autoencoders with sigmoid hidden units, the energy function is identical to the free energy of an RBM, which helps shed light onto the relationship between these two types of model. We also show that the autoencoder energy function allows us to explain common regularization procedures, such as contractive training, from the perspective of dynamical systems. As a practical application of the energy function, a generative classifier based on class-specific autoencoders is presented.

  15. HIGH ENERGY PHYSICS POTENTIAL AT MUON COLLIDERS

    SciTech Connect

    PARSA,Z.

    2000-04-07

    In this paper, high energy physics possibilities and future colliders are discussed. The {mu}{sup +} {mu}{sup {minus}} collider and experiments with high intensity muon beams as the stepping phase towards building Higher Energy Muon Colliders (HEMC) are briefly reviewed and encouraged.

  16. Quantum-Mechanical Calculation of Ionization-Potential Lowering in Dense Plasmas

    NASA Astrophysics Data System (ADS)

    Son, Sang-Kil; Thiele, Robert; Jurek, Zoltan; Ziaja, Beata; Santra, Robin

    2014-07-01

    The charged environment within a dense plasma leads to the phenomenon of ionization-potential depression (IPD) for ions embedded in the plasma. Accurate predictions of the IPD effect are of crucial importance for modeling atomic processes occurring within dense plasmas. Several theoretical models have been developed to describe the IPD effect, with frequently discrepant predictions. Only recently, first experiments on IPD in Al plasma have been performed with an x-ray free-electron laser, where their results were found to be in disagreement with the widely used IPD model by Stewart and Pyatt. Another experiment on Al, at the Orion laser, showed disagreement with the model by Ecker and Kröll. This controversy shows a strong need for a rigorous and consistent theoretical approach to calculate the IPD effect. Here, we propose such an approach: a two-step Hartree-Fock-Slater model. With this parameter-free model, we can accurately and efficiently describe the experimental Al data and validate the accuracy of standard IPD models. Our model can be a useful tool for calculating atomic properties within dense plasmas with wide-ranging applications to studies on warm dense matter, shock experiments, planetary science, inertial confinement fusion, and nonequilibrium plasmas created with x-ray free-electron lasers.

  17. The Calculation of Rotational Energy Levels Using Tunneling Hamiltonians

    NASA Astrophysics Data System (ADS)

    Hougen, Jon T.

    2009-06-01

    The present talk will present a pedagogical introduction and review of 25 years of using tunneling Hamiltonians to parameterize and fit rotationally resolved spectra of small polyatomic molecules with one or more large-amplitude motions (LAMs). This tunneling formalism does not require a quantitative knowledge of the potential surface, but instead makes use only of its symmetry properties. Topics planned for discussion include: the user communities for such Hamiltonians; the range of applicability and achievable accuracy; a representative list of molecules treated to date and their various combinations of internal-rotation, inversion, hydrogen-bond-exchange, and H-atom-transfer LAMs; a way of organizing the LAMs of these molecules in the mind using the piston-and-crankshaft vocabulary of the reciprocating engine; how the theoretical tools of point-groups, permutation-inversion groups, extended groups, and time reversal are used in the tunneling-Hamiltonian formalism; and finally a brief report on the present status of two unfinished applications of the tunneling-Hamiltonian formalism, namely cis/trans bent acetylene (HCCH) and protonated acetylene (C_2H_3^+).

  18. CONTINUOUS-ENERGY MONTE CARLO METHODS FOR CALCULATING GENERALIZED RESPONSE SENSITIVITIES USING TSUNAMI-3D

    SciTech Connect

    Perfetti, Christopher M; Rearden, Bradley T

    2014-01-01

    This work introduces a new approach for calculating sensitivity coefficients for generalized neutronic responses to nuclear data uncertainties using continuous-energy Monte Carlo methods. The approach presented in this paper, known as the GEAR-MC method, allows for the calculation of generalized sensitivity coefficients for multiple responses in a single Monte Carlo calculation with no nuclear data perturbations or knowledge of nuclear covariance data. The theory behind the GEAR-MC method is presented here, and proof of principle is demonstrated by using the GEAR-MC method to calculate sensitivity coefficients for responses in several 3D, continuous-energy Monte Carlo applications.

  19. Energy of Cohesion, Compressibility, and the Potential Energy Functions of the Graphite System

    NASA Technical Reports Server (NTRS)

    Girifalco, L. A.; Lad, R. A.

    1956-01-01

    The lattice summations of the potential energy of importance in the graphite system have been computed by direct summation assuming a Lennard-Jones 6-12 potential between carbon atoms. From these summations, potential energy curves were constructed for interactions between a carbon atom and a graphite monolayer, between a carbon atom and a graphite surface, between a graphite monolayer and a semi-infinite graphite crystal and between two graphite semi-infinite crystals. Using these curves, the equilibrium distance between two isolated physically interacting carbon atoms was found to be 2.70 a, where a is the carbon-carbon distance in a graphite sheet. The distance between a surface plane and the rest of the crystal was found to be 1.7% greater than the interlayer spacing. Theoretical values of the energy of cohesion and the compressibility were calculated from the potential curve for the interaction between two semi-infinite crystals. They were (delta)E(sub c) = -330 ergs/sq cm and beta =3.18x10(exp -12)sq cm/dyne, respectively. These compared favorably with the experimental values of (delta)E(sub c) = -260 ergs/sq cm and beta = 2.97 X 10(exp -2) sq cm/dyne.

  20. Self-consistent Calculation of the Quasi-particle Energy Spectrum of Sodium using the Correlated Hartree Fock Method

    NASA Astrophysics Data System (ADS)

    Ishihara, Takamitsu; Yamagami, Hiroshi; Yasuhara, Hiroshi

    2001-12-01

    Self-consistent band calculation of sodium is performed in the correlated Hartree Fock scheme proposed by Yasuhara and Takada [Phys. Rev. B 43 (1991) 7200], which contains information on the effective mass of the electron liquid in the form of a nonlocal spin-parallel potential, and the remaining information of the self-energy operator in the form of a local potential. The bandwidth of occupied states is somewhat increased under the influence of the non-local spin-parallel potential, compared with the free electron value. No significant difference can be found in the distortion of the Fermi surface between the present theory and the LDA.