Benchmark Calculations (benchmark + calculation)

Distribution by Scientific Domains

Selected Abstracts

ChemInform Abstract: Benchmark Calculations on the Electron Detachment Energies of MO3 - and M2O6 - (M: Cr, Mo, W)

CHEMINFORM, Issue 8 2008
Shenggang Li
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]

Non-empirical calculations of NMR indirect carbon,carbon coupling constants.

Monocycloalkanes, Part
Abstract Carbon,carbon and carbon,hydrogen spin,spin coupling constants were calculated in the series of the first six monocycloalkanes using SOPPA and SOPPA(CCSD) methods, and very good agreement with the available experimental data was achieved, with the latter method showing slightly better results in most cases, at least in those involving calculations of J(C,C). Benchmark calculations of all possible 21 coupling constants J(C,C), J(C,H) and J(H,H) in chair cyclohexane revealed the importance of using the appropriate level of theory and adequate quality of the basis sets. Many unknown couplings in this series were predicted with high confidence and several interesting structural trends (hybridization effects, multipath coupling transmission mechanisms, hyperconjugative interactions) were elucidated and are discussed based on the present calculations of spin,spin couplings. Copyright © 2004 John Wiley & Sons, Ltd. [source]

Validation of numerical codes for impact and explosion cratering: Impacts on strengthless and metal targets

When properly benchmarked and validated against observation, computer models offer a powerful tool for understanding the mechanics of impact crater formation. This work presents results from the first phase of a project to benchmark and validate shock codes. A variety of 2D and 3D codes were used in this study, from commercial products like AUTODYN, to codes developed within the scientific community like SOVA, SPH, ZEUS-MP, iSALE, and codes developed at U.S. National Laboratories like CTH, SAGE/RAGE, and ALE3D. Benchmark calculations of shock wave propagation in aluminum-on-aluminum impacts were performed to examine the agreement between codes for simple idealized problems. The benchmark simulations show that variability in code results is to be expected due to differences in the underlying solution algorithm of each code, artificial stability parameters, spatial and temporal resolution, and material models. Overall, the inter-code variability in peak shock pressure as a function of distance is around 10 to 20%. In general, if the impactor is resolved by at least 20 cells across its radius, the underestimation of peak shock pressure due to spatial resolution is less than 10%. In addition to the benchmark tests, three validation tests were performed to examine the ability of the codes to reproduce the time evolution of crater radius and depth observed in vertical laboratory impacts in water and two well-characterized aluminum alloys. Results from these calculations are in good agreement with experiments. There appears to be a general tendency of shock physics codes to underestimate the radius of the forming crater. Overall, the discrepancy between the model and experiment results is between 10 and 20%, similar to the inter-code variability. [source]

Parallel Fock matrix construction with distributed shared memory model for the FMO-MO method

Hiroaki Umeda
Abstract A parallel Fock matrix construction program for FMO-MO method has been developed with the distributed shared memory model. To construct a large-sized Fock matrix during FMO-MO calculations, a distributed parallel algorithm was designed to make full use of local memory to reduce communication, and was implemented on the Global Array toolkit. A benchmark calculation for a small system indicates that the parallelization efficiency of the matrix construction portion is as high as 93% at 1,024 processors. A large FMO-MO application on the epidermal growth factor receptor (EGFR) protein (17,246 atoms and 96,234 basis functions) was also carried out at the HF/6-31G level of theory, with the frontier orbitals being extracted by a Sakurai-Sugiura eigensolver. It takes 11.3 h for the FMO calculation, 49.1 h for the Fock matrix construction, and 10 min to extract 94 eigen-components on a PC cluster system using 256 processors. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010 [source]

Density functional computations of 99Ru chemical shifts: relativistic effects, influence of the density functional, and study of solvent effects on fac,[Ru(CO)3I3],

Jochen Autschbach
Abstract Solvent effects on the 99Ru NMR chemical shift of the complex fac,[Ru(CO)3I3], are investigated computationally using density functional theory. Further, benchmark calculations of the 99Ru shift for a set of ten Ru complexes have been performed in order to calibrate the computational model and to determine the importance of relativistic effects on the 99Ru nuclear magnetic shielding and on the chemical shift. A computational model for fac,[Ru(CO)3I3], that includes both explicit solvent molecules and a continuum model is shown to yield the best agreement with experiment. Relativistic corrections are shown to be of minor importance for determining 99Ru chemical shifts. On the other hand, the nature of the density functional is of importance. In agreement with literature data for ligand trends of 99Ru chemical shifts, the chemical shift range for different solvents is also best reproduced by a hybrid functional. Copyright © 2006 John Wiley & Sons, Ltd. [source]

The Risk-Adjusted Cost of Financial Distress

ABSTRACT Financial distress is more likely to happen in bad times. The present value of distress costs therefore depends on risk premia. We estimate this value using risk-adjusted default probabilities derived from corporate bond spreads. For a BBB-rated firm, our benchmark calculations show that the NPV of distress is 4.5% of predistress value. In contrast, a valuation that ignores risk premia generates an NPV of 1.4%. We show that marginal distress costs can be as large as the marginal tax benefits of debt derived by Graham (2000). Thus, distress risk premia can help explain why firms appear to use debt conservatively. [source]

Accounting for unresolved clouds in a 1-D solar radiative-transfer model

J. Li
Abstract New methods for the treatment of solar radiative transfer through overlapping and inhomogeneous clouds are presented. First, a new approach to cloud overlap is shown. For the adjacent cloud blocks, the traditional maximum overlap can be relaxed to a mixture of maximum and random overlap treatments for layers that are adjacent but not fully correlated. Second, a new radiative-transfer algorithm has been developed to deal with these various cloud overlap circumstances that is simple enough for implementation in a general-circulation model (GCM). When compared to appropriate benchmark calculations, we find that this new method can produce accurate results in heating rates and fluxes with relative errors generally less than 8%. Third, a new and very simple approach to treating radiative transfer through a cloud with horizontal subgrid-scale inhomogeneities is developed. This approach uses an optical-depth scaling technique to represent the subgrid-scale inhomogeneity. Finally, by combining all of the above elements, we provide a new algorithm for the combined treatment of cloud overlap and inhomogeneity and we show that it yields very reasonable accuracies for heating rates and fluxes. Through benchmark comparisons, we show that this new algorithm provides significant improvement over existing schemes in GCMs. Copyright © 2005 Royal Meteorological Society [source]

DFT/CCSD(T) Investigation of the Interaction of Molecular Hydrogen with Carbon Nanostructures

CHEMPHYSCHEM, Issue 11 2009
Miroslav Rube
Abstract The interaction of molecular hydrogen with carbon nanostructures is investigated within the DFT/CC correction scheme. The DFT/CC results are compared with the benchmark calculations at the CCSD(T) level of theory for benzene and naphthalene, and at the MP2 level for the more extended systems. The DFT/CC method offers a reliable alternative to the highly correlated ab initio calculations at a cost comparable to the standard DFT method. The results for H2 adsorbed on graphene as well as single-wall carbon nanotubes (SWCNT) are presented. The DFT/CC binding energy on graphene of 5.4 kJ,mol,1 is in good agreement with experiment (5.00±0.05 kJ,mol,1). For (10,10)-SWCNT, the H2 molecule is mostly stabilized inside the tube with an estimated binding energy of 7.2 kJ,mol,1. [source]

Ab initio Study of the Interactions between CO2 and N-Containing Organic Heterocycles

CHEMPHYSCHEM, Issue 2 2009
Konstantinos D. Vogiatzis
Abstract In the garden of dispersion: High-accuracy ab initio calculations are performed to determine the nature of the interactions and the most favorable geometries between CO2 and heteroaromatic molecules containing nitrogen (see figure). Dispersion forces play a key role in the stabilization of the dimer, because correlation effects represent about 50,% of the total interaction energy. The interactions between carbon dioxide and organic heterocyclic molecules containing nitrogen are studied by using high-accuracy ab initio methods. Various adsorption positions are examined for pyridine. The preferred configuration is an in-plane configuration. An electron donor,electron acceptor (EDA) mechanism between the carbon of CO2 and the nitrogen of the heterocycle and weak hydrogen bonds stabilize the complex, with important contributions from dispersion and induction forces. Quantitative results of the binding energy of CO2 to pyridine (C5H5N), pyrimidine, pyridazine, and pyrazine (C4H4N2), triazine (C3H3N3), imidazole (C3H4N2), tetrazole (CH2N4), purine (C5H4N4), imidazopyridine (C6H5N3), adenine (C5H5N5), and imidazopyridamine (C6H6N4) for the in-plane configuration are presented. For purine, three different binding sites are examined. An approximate coupled-cluster model including single and double excitations with a perturbative estimation of triple excitations (CCSD(T)) is used for benchmark calculations. The CCSD(T) basis-set limit is approximated from explicitly correlated second-order Møller,Plesset (MP2-F12) calculations in the aug-cc-pVTZ basis in conjunction with contributions from single, double, and triple excitations calculated at the CCSD(T)/6-311++G** level of theory. Extrapolations to the MP2 basis-set limit coincide with the MP2-F12 calculations. The results are interpreted in terms of electrostatic potential maps and electron density redistribution plots. The effectiveness of density functional theory with the empirical dispersion correction of Grimme (DFT-D) is also examined. [source]