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Møller-Plesset Perturbation Theory (møller-plesset + perturbation_theory)
Selected AbstractsRelativistic and electron-correlation effects on magnetizabilities investigated by the Douglas-Kroll-Hess method and the second-order Møller-Plesset perturbation theoryJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 15 2009Terutaka Yoshizawa Abstract Isotropic and anisotropic magnetizabilities for noble gas atoms and a series of singlet and triplet molecules were calculated using the second-order Douglas-Kroll-Hess (DKH2) Hamiltonian containing the vector potential A and in part using second-order generalized unrestricted Møller-Plesset (GUMP2) theory. The DKH2 Hamiltonian was resolved into three parts (spin-free terms, spin-dependent terms, and magnetic perturbation terms), and the magnetizabilities were decomposed into diamagnetic and paramagnetic terms to investigate the relativistic and electron-correlation effects in detail. For Ne, Kr, and Xe, the calculated magnetizabilities approached the experimental values, once relativistic and electron-correlation effects were included. For the IF molecule, the magnetizability was strongly affected by the spin-orbit interaction, and the total relativistic contribution amounted to 22%. For group 17, 16, 15, and 14 hydrides, the calculated relativistic effects were small (less than 3%), and trends were observed in relativistic and electron-correlation effects across groups and periods. The magnetizability anisotropies of triplet molecules were generally larger than those of similar singlet molecules. The so-called relativistic-correlation interference for the magnetizabilities computed using the relativistic GUMP2 method can be neglected for the molecules evaluated, with exception of triplet SbH. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009 [source] An improved algorithm for analytical gradient evaluation in resolution-of-the-identity second-order Møller-Plesset perturbation theory: Application to alanine tetrapeptide conformational analysisJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 5 2007Robert A. Distasio JR. Abstract We present a new algorithm for analytical gradient evaluation in resolution-of-the-identity second-order Møller-Plesset perturbation theory (RI-MP2) and thoroughly assess its computational performance and chemical accuracy. This algorithm addresses the potential I/O bottlenecks associated with disk-based storage and access of the RI-MP2 t -amplitudes by utilizing a semi-direct batching approach and yields computational speed-ups of approximately 2,3 over the best conventional MP2 analytical gradient algorithms. In addition, we attempt to provide a straightforward guide to performing reliable and cost-efficient geometry optimizations at the RI-MP2 level of theory. By computing relative atomization energies for the G3/99 set and optimizing a test set of 136 equilibrium molecular structures, we demonstrate that satisfactory relative accuracy and significant computational savings can be obtained using Pople-style atomic orbital basis sets with the existing auxiliary basis expansions for RI-MP2 computations. We also show that RI-MP2 geometry optimizations reproduce molecular equilibrium structures with no significant deviations (>0.1 pm) from the predictions of conventional MP2 theory. As a chemical application, we computed the extended-globular conformational energy gap in alanine tetrapeptide at the extrapolated RI-MP2/cc-pV(TQ)Z level as 2.884, 4.414, and 4.994 kcal/mol for structures optimized using the HF, DFT (B3LYP), and RI-MP2 methodologies and the cc-pVTZ basis set, respectively. These marked energetic discrepancies originate from differential intramolecular hydrogen bonding present in the globular conformation optimized at these levels of theory and clearly demonstrate the importance of long-range correlation effects in polypeptide conformational analysis. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007 [source] Systematic quantum chemical study of DNA-base tautomersJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 1 2004M. Piacenza Abstract The relative energies of the energetically low-lying tautomers of pyridone, cytosine, uracil, thymine, guanine, and iso-cytosine are studied by a variety of different quantum chemical methods. In particular, we employ density functional theory (DFT) using the six functionals HCTH407, PBE, BP86, B-LYP, B3-LYP, and BH-LYP, and the ab initio methods Hartree-Fock (HF), standard second-order Møller-Plesset perturbation theory (MP2), an improved version of it (SCS-MP2), and quadratic configuration interaction including single and double excitations (QCISD) and perturbative triple corrections [QCISD(T)]. A detailed basis set study is performed for the formamide/formamidic acid tautomeric pair. In general, large AO basis sets of at least valence triple-, quality including f-functions (TZV) are employed, which are found to be necessary for an accurate energetic description of the various structures. The performance of the more approximate methods is evaluated with QCISD(T)/TZV(2df,2dp) data taken as reference. In general it is found that DFT is not an appropriate method for the problem. For the tautomers of pyridone and cytosine, most density functionals, including the popular B3-LYP hybrid, predict a wrong energetic order, and only for guanine, the correct sequence of tautomers is obtained with all functionals. Out of the density functionals tested, BH-LYP, which includes a rather large fraction of HF exchange, performs best. A consistent description of the nonaromatic versus aromatic tautomers seems to be a general problem especially for pure, nonhybrid functionals. Tentatively, this could be assigned to the exchange potentials used while the functional itself, including the correlation part, seems to be appropriate. Out of the ab initio methods tested, the new SCS-MP2 approach seems to perform best because it effectively reduces some outliers obtained with standard MP2. It outperforms the much more costly QCISD method and seems to be a very good compromise between computational effort and accuracy. © 2003 Wiley Periodicals, Inc. J Comput Chem 1: 83,98, 2004 [source] Calculation of the Detonation Velocities and Detonation Pressures of Dinitrobiuret (DNB) and Diaminotetrazolium Nitrate (HDAT-NO3)PROPELLANTS, EXPLOSIVES, PYROTECHNICS, Issue 1 2004Janna Geith Abstract The enthalpies of combustion (,combH) of dinitrobiuret (DNB) and diaminotetrazolium nitrate (HDAT-NO3) were determined experimentally using oxygen bomb calorimetry: ,combH(DNB)=5195±200,kJ kg,1, ,combH(HDAT-NO3)=7900±300,kJ kg,1. The standard enthalpies of formation (,fH°) of DNB and HDAT-NO3 were obtained on the basis of quantum chemical computations at the electron-correlated ab initio MP2 (second order Møller-Plesset perturbation theory) level of theory using a correlation consistent double-zeta basis set (cc-pVTZ): ,fH°(DNB)=,353,kJ mol,1, ,1,829,kJ kg,1; ,fH°(HDAT-NO3)=+254,kJ mol,1, +1,558,kJ kg,1. The detonation velocities (D) and detonation pressures (P) of DNB and HDAT-NO3 were calculated using the empirical equations by Kamlet and Jacobs: D(DNB)=8.66,mm,,s,1, P(DNB)=33.9,GPa, D(HDAT-NO3)=8.77,mm,,s,1, P(HDAT-NO3)=33.3,GPa. [source] | ||||||||||