Systematic coarse-graining of nanoparticle interactions in molecular dynamics simulation

A recently developed multiscale coarse-graining procedure [Izvekov, S.; Voth, G. A. J. Phys. Chem. B 2005, 109, 2469] is extended to derive coarse-grained models for nanoparticles. The methodology is applied to C(60) and to carbonaceous nanoparticles produced in combustion environments. The coarse-graining of the interparticle force field is accomplished applying a force-matching procedure to data obtained from trajectories and forces from all-atom MD simulations. The CG models are shown to reproduce accurately the structural properties of the nanoparticle systems studied, while allowing for MD simulations of much larger self-assembled nanoparticle systems.     

Mixed atomistic and coarse-grained molecular dynamics: simulation of a membrane-bound ion channel

The recently developed multiscale coarse-graining (MS-CG) method (Izvekov, S.; Voth, G. A. J. Phys. Chem. B 2005, 109, 2469; J. Chem. Phys. 2005, 123, 134105) is used to build a mixed all-atom and coarse-grained (AA-CG) model of the gramicidin A (gA) ion channel embedded in a dimyristoylphosphatidylcholine (DMPC) lipid bilayer and water environment. In this model, the gA peptide was described in full atomistic detail, while the lipid and water molecules were described using coarse-grained representations. The atom-CG and CG-CG interactions in the mixed AA-CG model were determined using the MS-CG method. Molecular dynamics (MD) simulations were performed using the resulting AA-CG model. The results from simulations of the AA-CG model compare very favorably to those from all-atom MD simulations of the entire system. Since the MS-CG method employs a general and systematic approach to obtain effective interactions from the underlying all-atom models, the present approach to rigorously develop mixed AA-CG models has the potential to be extended to many other systems.     

Bound state potential energy surface construction: ab initio zero-point energies and vibrationally averaged rotational constants

Collins' method of interpolating a potential energy surface (PES) from quantum chemical calculations for reactive systems (Jordan, M. J. T.; Thompson, K. C.; Collins, M. A. J. Chem. Phys. 1995, 102, 5647. Thompson, K. C.; Jordan, M. J. T.; Collins, M. A. J. Chem. Phys. 1998, 108, 8302. Bettens, R. P. A.; Collins, M. A. J. Chem. Phys. 1999, 111, 816) has been applied to a bound state problem. The interpolation method has been combined for the first time with quantum diffusion Monte Carlo calculations to obtain an accurate ground state zero-point energy, the vibrationally average rotational constants, and the vibrationally averaged internal coordinates. In particular, the system studied was fluoromethane using a composite method approximating the QCISD(T)/6-311++G(2df,2p) level of theory. The approach adopted in this work (a) is fully automated, (b) is fully ab initio, (c) includes all nine nuclear degrees of freedom, (d) requires no assumption of the functional form of the PES, (e) possesses the full symmetry of the system, (f) does not involve fitting any parameters of any kind, and (g) is generally applicable to any system amenable to quantum chemical calculations and Collins' interpolation method. The calculated zero-point energy agrees to within 0.2% of its current best estimate. A0 and B0 are within 0.9 and 0.3%, respectively, of experiment.     

Molecular dynamics simulation of the dielectric constant of water: the effect of bond flexibility

The role of bond flexibility on the dielectric constant of water is investigated via molecular dynamics simulations using a flexible intermolecular potential SPC/Fw [Y. Wu, H. L. Tepper, and G. A. Voth, J. Chem. Phys. 128, 024503 (2006)]. Dielectric constants and densities are reported for the liquid phase at temperatures of 298.15 K and 473.15 K and the supercritical phase at 673.15 K for pressures between 0.1 MPa and 200 MPa. Comparison with both experimental data and other rigid bond intermolecular potentials indicates that introducing bond flexibility significantly improves the prediction of both dielectric constants and pressure-temperature-density behavior. In some cases, the predicted densities and dielectric constants almost exactly coincide with experimental data. The results are analyzed in terms of dipole moments, quadrupole moments, and equilibrium bond angles and lengths. It appears that bond flexibility allows the molecular dipole and quadrupole moment to change with the thermodynamic state point, and thereby mimic the change of the intermolecular interactions in response to the local environment.     

Liquid crystal properties of the n-alkyl-cyanobiphenyl series from atomistic simulations with ab initio derived force fields

Lengthy molecular dynamics (MD) simulations were performed at constant atmospheric pressure and different temperatures for the series of the 4-n-alkyl-4'-cyanobiphenyls (nCB) with n = 6, 7, and 8. The accurate atomistic force field (Bizzarri, M.; Cacelli, I.; Prampolini, G; Tani, A. J. Phys. Chem. A 2004, 108, 10336), successfully employed to reproduce thermodynamic and transport properties of the 5CB molecule, has here been extended to higher homologues. Nematic and isotropic phases were found for all members of the series, and also, a smectic phase was (tentatively) identified for 8CB at 1 atm and 300 K. Transition temperatures reproduce the experimental values within +/-10 K. Also, structural properties as second and fourth rank orientational order parameters are in good agreement with the corresponding experimental quantities. This means that the well-known odd-even effect, observed for many properties along the nCB series, is well reproduced, despite the narrow range of oscillations, e.g., in clearing temperatures. A detailed analysis of the correlation between molecular properties and odd-even effects is presented.     

Molecular dynamics simulations of PAMAM dendrimer-induced pore formation in DPPC bilayers with a coarse-grained model

We have performed 0.5-micros-long molecular dynamics (MD) simulations of 0%, 50%, and 100% acetylated third- (G3) and fifth-generation (G5) polyamidoamine (PAMAM) dendrimers in dipalmitoylphosphatidylcholine (DPPC) bilayers with explicit water using the coarse-grained (CG) model developed by Marrink et al. (J.Phys. Chem. B 2004, 108, 750-760), but with long-range electrostatic interactions included. Radii of gyration of the CG G5 dendrimers are 1.99-2.32 nm, close to those measured in the experiments by Prosa et al. (J. Polym. Sci. 1997, 35, 2913-2924) and atomistic simulations by Lee et al. (J. Phys. Chem. B 2006, 110, 4014-4019). Starting with the dendrimer initially positioned near the bilayer, we find that positively charged un-acetylated G3 and 50%-acetylated and un-acetylated G5 dendrimers insert themselves into the bilayer, and only un-acetylated G5 dendrimer induces hole formation at 310 K, but not at 277 K, which agrees qualitatively with experimental observations of Hong et al. (Bioconj. Chem. 2004, 15, 774-782) and Mecke et al. (Langmuir 2005, 21, 10348-10354). At higher salt concentration (approximately 500 mM NaCl), un-acetylated G5 dendrimer does not insert into the bilayer. The results suggest that with inclusion of long-range electrostatic interactions into coarse-grained models, realistic MD simulation of membrane-disrupting effects of nanoparticles at the microsecond time scale is now possible.     

Multiscale coarse-graining and structural correlations: connections to liquid-state theory

A statistical mechanical framework elucidates the significance of structural correlations between coarse-grained (CG) sites in the multiscale coarse-graining (MS-CG) method (Izvekov, S.; Voth, G. A. J. Phys. Chem. B 2005, 109, 2469; J. Chem. Phys. 2005, 123, 134105). If no approximations are made, then the MS-CG method yields a many-body multidimensional potential of mean force describing the interactions between CG sites. However, numerical applications of the MS-CG method typically employ a set of pair potentials to describe nonbonded interactions. The analogy between coarse-graining and the inverse problem of liquid-state theory clarifies the general significance of three-particle correlations for the development of such CG pair potentials. It is demonstrated that the MS-CG methodology incorporates critical three-body correlation effects and that, for isotropic homogeneous systems evolving under a central pair potential, the MS-CG equations are a discretized representation of the well-known Yvon-Born-Green equation. Numerical calculations validate the theory and illustrate the role of these structural correlations in the MS-CG method.     

Evaluation of data for atmospheric models: master equation/RRKM calculations on the combination reaction, BrO + NO2 --> BrONO2, a conundrum

Experimental data for the title reaction were modeled using master equation (ME)/RRKM methods based on the Multiwell suite of programs. The starting point for the exercise was the empirical fitting provided by the NASA (Sander, S. P.; Finlayson-Pitts, B. J.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Molina, M. J.; Moortgat, G. K.; Orkin, V. L.; Ravishankara, A. R. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15; Jet Propulsion Laboratory: Pasadena, California, 2006)1 and IUPAC (Atkinson, R.; Baulch, D. L.; Cox, R. A.; R. F. Hampson, J.; Kerr, J. A.; Rossi, M. J.; Troe, J. J. Phys. Chem. Ref. Data 2000, 29, 167)2 data evaluation panels, which represents the data in the experimental pressure ranges rather well. Despite the availability of quite reliable parameters for these calculations (molecular vibrational frequencies (Parthiban, S.; Lee, T. J. J. Chem. Phys. 2000, 113, 145)3 and a value (Orlando, J. J.; Tyndall, G. S. J. Phys. Chem. 1996, 100, 19398)4 of the bond dissociation energy, D298(BrO-NO2) = 118 kJ mol-1, corresponding to DeltaH0o = 114.3 kJ mol-1 at 0 K) and the use of RRKM/ME methods, fitting calculations to the reported data or the empirical equations was anything but straightforward. Using these molecular parameters resulted in a discrepancy between the calculations and the database of rate constants of a factor of ca. 4 at, or close to, the low-pressure limit. Agreement between calculation and experiment could be achieved in two ways, either by increasing DeltaH0o to an unrealistically high value (149.3 kJ mol-1) or by increasing DeltaEd, the average energy transferred in a downward collision, to an unusually large value (>5000 cm-1). The discrepancy could also be reduced by making all overall rotations fully active. The system was relatively insensitive to changing the moments of inertia in the transition state to increase the centrifugal effect. The possibility of involvement of BrOONO was tested and cannot account for the difficulties of fitting the data.     

From homogeneous dispersion to micelles-a molecular dynamics simulation on the compromise of the hydrophilic and hydrophobic effects of sodium dodecyl sulfate in aqueous solution

The structural and functional diversity of surfactant systems has attracted simulation works in atomistic, coarse grain, and mesoscopic models (Bandyopadhyay, S.; et al. Langmuir 2000, 16, 942; Senapati, S.; et al. J. Phys. Chem. B 2003, 107, 12906; Maiti, P. K.; et al. Langmuir 2002, 18, 1908; Srinivas, G.; et al. J. Phys. Chem. B 2004, 108, 8153; Groot, R. D.; et al. J. Chem. Phys. 1999, 110, 9739; Rekvig, L.; et al. Langmuir 2003, 19, 8195). However, atomistic models have suffered from their tremendous computational cost and are, so far, not able to simulate the structural behaviors in sufficient spatio-temporal scales (Shelley, J. C.; Shelley, M. Y. Curr. Opin. Colloid Interface Sci. 2000, 5, 101). The other two approaches are not microscopic enough to describe the configurations of the surfactants that determine their behaviors (Shelley and Shelley). In this study, we propose to simplify atomistic models based on the observation that the compromise of the hydrophilic and hydrophobic effects (Li, J.; Kwauk, M. Chem. Eng. Sci. 2003, 58, 521-535) and molecular structures of surfactants are the dominant factors shaping their structures in the systems. With this simplification, we are able to simulate with moderate computing cost the whole process of micelle formation from an initially uniform dispersion of sodium dodecyl sulfate (SDS) in aqueous solution. The resulting micelle structures are different from those predicted by atomistic simulations that started with a predefined micelle configuration at the same surfactant concentrations. However, if we use their initial micelle configuration, micelle structures the same as theirs are obtained. Analyses show that our results are more realistic and that the results of the atomistic simulations suffer from artificial initial conditions. Therefore, our model may serve as a reasonable simplification of atomistic models in terms of the general structure of micelles.     

Reaction of OH + NO2: high pressure experiments and falloff analysis

High pressure experiments on the OH + NO2 reaction are presented for 3 different temperatures. At 300 K, experiments in He (p = 2-500 bar) as well as in Ar (p = 2-4 bar) were performed. The rate constants obtained in Ar agree well with values which have been reported earlier by our group (Forster, R.; Frost, M.; Fulle, D.; Hamann, H. F.; Hippler, H.; Schlepegrell, A.; Troe, J. J. Chem. Phys. 1995, 103, 2949. Fulle, D.; Hamann, H. F.; Hippler, H.; Troe, J. J. Chem. Phys. 1998, 108, 5391). In contrast, the rate coefficients determined in He were found to be 15-25% lower than the values given in our earlier publications. Additionally, results for He as bath gas at elevated temperatures (T = 400 K, p = 3-150 bar; T = 600 K, p = 3-150 bar) are reported. The results obtained at elevated pressures are found to be in good agreement with existing literature data. The observed falloff behavior is analyzed in terms of the Troe formalism taking into account two reaction channels: one yielding HNO3 and one yielding HOONO. It is found that the extracted parameters are in agreement with rate constants for vibrational relaxation and isotopic scrambling as well as with experimentally determined branching ratios. Based on our analysis we determine falloff parameters to calculate the rate constant for atmospheric conditions.     

Towards an understanding of many-particle effects in hydrophobic association in methane solutions

This paper applies the multiscale coarse-graining method [S. Izvekov and G. A. Voth, J. Phys. Chem. B 109, 2469 (2005); J. Chem. Phys. 123, 134105 (2005)] to analyze many-body effects in concentrated methane solutions. Pairwise decompositions of N-particle solute-solute potentials of mean force (PMFs), and the respective solvent cavity potentials, enthalpic, entropic, and heat capacity of hydrophobic association, are calculated directly from unconstrained molecular-dynamics simulations of methane solutions at different molar fractions, with the highest being 0.055. The many-body effects in hydrophobic hydration are further studied using N-methane PMFs, which are explicitly dependent on solvent coordinates.     

Luminescence and Raman spectra of acetylacetone at low temperatures

Raman spectra of acetylacetone were recorded for molecules isolated in an argon matrix at 10 K and for a polycrystalline sample. In the solid sample, broad bands appear superimposed on a much weaker Raman spectrum corresponding mainly to the stable enol form. The position of these bands depends on the excitation wavelength (514.5 and 488.8 nm argon ion laser lines were used), sample temperature, and cooling history. They are attributed to transitions from an excited electronic state to various isomer states in the ground electronic state. Laser photons have energies comparable to energies of a number of excited triplet states predicted for a free acetylacetone molecule (Chen, X.-B.; Fang, W.-H.; Phillips, D. L. J. Phys. Chem. A 2006, 110, 4434). Since singlet-to-triplet photon absorption transitions are forbidden, states existing in the solid have mixed singlet/triplet character. Their decay results in population of different isomer states, which except for the lowest isomers SYN enol, TS2 enol (described in Matanovi? I.; Dosli?, N. J. Phys. Chem. A 2005, 109, 4185), and the keto form, which can be detected in the Raman spectra of the solid, are not vibrationally resolved. Differential scanning calorimetry detected two signals upon cooling of acetylacetone, one at 229 K and one at 217 K, while upon heating, they appear at 254 and 225 K. The phase change at higher temperature is attributed to a freezing/melting transition, while the one at lower temperature seems to correspond to freezing/melting of keto domains, as suggested by Johnson et al. (Johnson, M. R.; Jones, N. H.; Geis, A; Horsewill. A. J.; Trommsdorff, H. P. J. Chem. Phys. 2002, 116, 5694). Using matrix isolation in argon, the vibrational spectrum of acetylacetone at 10 K was recorded. Strong bands at 1602 and 1629 cm(-1) are assigned as the SYN enol bands, while a weaker underlying band at 1687 cm(-1) and a medium shoulder at 1617 cm(-1) are assigned as TS2 enol bands.     

The multiscale coarse-graining method. II. Numerical implementation for coarse-grained molecular models

The multiscale coarse-graining (MS-CG) method [S. Izvekov and G. A. Voth, J. Phys. Chem. B 109, 2469 (2005); J. Chem. Phys. 123, 134105 (2005)] employs a variational principle to determine an interaction potential for a CG model from simulations of an atomically detailed model of the same system. The companion paper proved that, if no restrictions regarding the form of the CG interaction potential are introduced and if the equilibrium distribution of the atomistic model has been adequately sampled, then the MS-CG variational principle determines the exact many-body potential of mean force (PMF) governing the equilibrium distribution of CG sites generated by the atomistic model. In practice, though, CG force fields are not completely flexible, but only include particular types of interactions between CG sites, e.g., nonbonded forces between pairs of sites. If the CG force field depends linearly on the force field parameters, then the vector valued functions that relate the CG forces to these parameters determine a set of basis vectors that span a vector subspace of CG force fields. The companion paper introduced a distance metric for the vector space of CG force fields and proved that the MS-CG variational principle determines the CG force force field that is within that vector subspace and that is closest to the force field determined by the many-body PMF. The present paper applies the MS-CG variational principle for parametrizing molecular CG force fields and derives a linear least squares problem for the parameter set determining the optimal approximation to this many-body PMF. Linear systems of equations for these CG force field parameters are derived and analyzed in terms of equilibrium structural correlation functions. Numerical calculations for a one-site CG model of methanol and a molecular CG model of the EMIM(+)NO(3) (-) ionic liquid are provided to illustrate the method.     

Modeling real dynamics in the coarse-grained representation of condensed phase systems

This work presents a systematic multiscale methodology to provide a more faithful representation of real dynamics in coarse-grained molecular simulation models. The theoretical formalism is based on the recently developed multiscale coarse-graining (MS-CG) method [S. Izvekov and G. A. Voth, J. Phys. Chem. B. 109, 2469 (2005); J. Chem. Phys. 123, 134105 (2005)] and relies on the generalized Langevin equation approach and its simpler Langevin equation limit. The friction coefficients are determined in multiscale fashion from the underlying all-atom molecular dynamics simulations using force-velocity and velocity-velocity correlation functions for the coarse-grained sites. The diffusion properties in the resulting CG Brownian dynamics simulations are shown to be quite accurate. The time dependence of the velocity autocorrelation function is also well-reproduced relative to the all-atom model if sufficient resolution of the CG sites is implemented.     

Molecular nitrogen-N2 properties: the intermolecular potential and the equation of state

Quantum mechanical (QM) high precision calculations were used to determine N(2)-N(2) intermolecular interaction potential. Using QM numerical data the anisotropic potential energy surface was obtained for all orientations of the pair of the nitrogen molecules in the rotation invariant form. The new N(2)-N(2) potential is in reasonably good agreement with the scaled potential obtained by van der Avoird et al. using the results of Hartree-Fock calculations [J. Chem. Phys. 84, 1629 (1986)]. The molecular dynamics (MD) of the N(2) molecules has been used to determine nitrogen equation of state. The classical motion of N(2) molecules was integrated in rigid rotor approximation, i.e., it accounted only translational and rotational degrees of freedom. Fincham [Mol. Simul. 11, 79 (1993)] algorithm was shown to be superior in terms of precision and energy stability to other algorithms, including Singer [Mol. Phys. 33, 1757 (1977)], fifth order predictor-corrector, or Runge-Kutta, and was therefore used in the MD modeling of the nitrogen pressure [S. Krukowski and P. Strak, J. Chem. Phys. 124, 134501 (2006)]. Nitrogen equation of state at pressures up to 30 GPa (300 kbars) and temperatures from the room temperature to 2000 K was obtained using MD simulation results. Results of MD simulations are in very good agreement (the error below 1%) with the experimental data on nitrogen equation of state at pressures below 1 GPa (10 kbars) for temperatures below 1800 K [R. T. Jacobsen et al., J. Phys. Chem. Ref. Data 15, 735 (1986)]. For higher temperatures, the deviation is slightly larger, about 2.5% which still is a very good agreement. The slightly larger difference may be attributed to the vibrational motion not accounted explicitly by rigid rotor approximation, which may be especially important at high temperatures. These results allow to obtain reliable equation of state of nitrogen for pressures up to 30 GPa (300 kbars), i.e., close to molecular nitrogen stability limit, determined by Nellis et al. [Phys. Rev. Lett. 53, 1661 (1984)].     

Kinetic restriction of simple gases in porous carbons: transition-state theory study

The separation of simple gases such as N2, Ar, CO2, and CH4 is an industrially important problem, particularly for the mitigation of greenhouse emissions. Furthermore, these gases are widely accepted as standard probing gases for the characterization of the microstructure of porous solids. However, a consistent set of microstructural parameters of a microporous solid determined from the use of adsorption measurements of these different gases is not always achieved because of differences in their pore accessibility. This is a long-standing and poorly understood problem. Here, we present the calculated results of the crossing time of N2, Ar, CO2, and CH4 between two neighboring cages through a constricted window in a realistic structural model of saccharose char, generated from hybrid reverse Monte Carlo (HRMC) simulation (Nguyen, T. X.; Bhatia, S. K.; Jain, S. K.; Gubbins, K. E. Mol. Simul. 2006, 32, 567-577) using transition state theory (TST), as described in our recent work (Nguyen, T. X.; Bhatia, S. K. J. Phys. Chem. 2007, 111, 2212-2222). The striking feature in these results is that whereas very fast diffusion of carbon dioxide within the temperature range of 273-343 K, with crossing time on the molecular dynamics scale (10-4-10-6 s), leads to instantaneous equilibrium and no hysteresis on the experimental time scale, slower diffusion of Ar and N2 at the low temperature of analysis indicates an accessibility problem. These results rationalize the experimental results of hysteresis for N2 at 77 K and Ar at 87 K but not for CO2 at 273 K in Takeda 3 A carbon molecular sieves. Furthermore, it is shown that CH4 diffusion through narrow pore mouths can be hindered even at ambient temperature. Finally, we show that the use of pore size and wall thickness distributions extracted from the adsorption of Ar at 87 K using the finite wall thickness (FWT) model (Nguyen, T. X.; Bhatia, S. K. Langmuir 2004, 20, 3532-3535 and Nguyen, T. X.; Bhatia, S. K. J. Phys. Chem. B 2004, 108, 14032-14042) provides the correct prediction of experimental CO2 adsorption in BPL and PCB carbons whereas that from N2 at 77 K gives a significant underprediction for both CO2 and CH4 in the BPL carbon. These trends are in excellent agreement with those predicted using the calculated crossing times.     

Ab initio equation of state of an organic molecular crystal: 1,1-diamino-2,2-dinitroethylene

A complete equation of state for the molecular crystal 1,1-diamino-2,2-dinitroethylene has been calculated from first principles for temperatures between 0 and 400 K, and for specific volumes from 61 to 83 cm3/mol, corresponding to relative volumes from 0.78 to 1.06. The calculated 300 K isotherm agrees very well with the experimentally measured pressure-volume relation reported by Peiris et al. (Peiris, S. M.; Wong, C. P.; Zerilli, F. J. J. Chem. Phys. 2004, 120, 8060). The volumetric thermal expansion coefficient is calculated to be 140 ppm/K at 300 K and atmospheric pressure and varies considerably with specific volume as well as temperature. The Grüneisen parameter varies significantly with temperature, but its variation with specific volume is small. The calculated specific heat (160 J/mol/K at 300 K and atmospheric pressure) has only a very small dependence on specific volume.     

Nonlinear elasticity and yielding of nanoparticle glasses

We employ experiment and theory to explore the nonlinear elasticity and yielding of concentrated suspensions of nanoparticles which interact via purely repulsive forces. These glassy suspensions are found to exhibit high exponent power law or simple exponential dependences of the shear elastic modulus and perturbative yield stress on nanoparticle volume fraction, as well as a monotonic decrease of the perturbative yield strain with increasing concentration. Our experimental observations are in good agreement with the predictions of a recently developed microscopic statistical mechanical theory, which describes glassy dynamics based on a nonequilibrium free energy that incorporates local cage correlations and activated barrier hopping processes [(1) Schweizer, K. S.; Saltzman, E. J. J. Chem. Phys. 2003, 119, 1181. (2) Saltzman, E. J.; Schweizer, K. S. J. Chem. Phys. 2003, 119, 1197. (3) Kobelev, V.; Schweizer, K. S. Phy. Rev. E 2005, 71, 021401].     

The reaction OH + C2H4: an example of rotational channel switching

The low-temperature data for the reaction between OH and C(2)H(4) is treated canonically as either a two-well or one-well problem using the "Multiwell" suite of codes, in which a "well" refers to a minimum in the potential energy surface. The former is analogous to the two transition state model of Greenwald et al. [Greenwald, E. E.; North, S. W.; Georgievskii, Y.; Klippenstein, S. J. J. Phys. Chem. A2005, 109, 6031], while the latter reflects the dominance of the so-called "inner transition state". External rotations are treated adiabatically, causing changes in the magnitude of effective barriers as a function of temperature. Extant data are well-described with either model using only the average energy transferred in a downward direction, upon collision, ΔE(d)(T), as a fitting parameter. The best value for the parameters describing the rate coefficient as a function of temperature (200 < T/K < 400) (Data at lower temperature is too sparse to yield a recommendation.) and pressure in the form used in the NASA/JPL format [Sander, S. P.; Abbatt, J.; Barker, J. R.; Burkholder, J. B.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Moortgat, G. K et al., Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 17, Jet Propulsion Laboratory, 2011] are k(0) = 1.0 × 10(-28)(T/300)(-3.5) cm(6) molecule(-2) s(-1) and k(∞) to 8.0 × 10(-12)(T/300)(-2.3) cm(3) molecule(-1) s(-1).     

New reaction simulator "LUMMOX" and its application for prediction of catalytic activities

We developed a new reaction simulator, "LUMMOX." It is an intermolecular interaction analyzer based on the theories of paired interacting orbitals (PIOs) and localized frontier orbitals (LFOs) that have been developed by Fujimoto et al. (Fukui, K.; Koga, N.; Fujimoto, H. J Am Chem Soc 1981, 103, 196; Fujimoto, H.; Koga, N.; Fukui, K. J Am Chem Soc 1981, 103, 7452; Fujimoto, H.; Satoh, S. J Phys Chem 1994, 98, 1436). LUMMOX runs on a Windows PC and displays graphic representation of orbital interactions. Prediction of activities, selectivities, and molecular weight of olefin polymerization catalysts are presented using PIO analysis and LFO calculation. Not only computational chemists but also experimental chemists can easily use this new system for catalyst design or molecular design from the point of view of orbital interaction.