Accurate Quantum‐Chemical Prediction of Enthalpies of Formation of Small Molecules in the Gas Phase

The coupled‐cluster approach, including single and double excitations and perturbative corrections for triple excitations, is capable of predicting molecular electronic energies and enthalpies of formation of small molecules in the gas phase with very high accuracy (specifically, with error bars less than 5 kJ mol^?1), provided that the electronic wavefunction is dominated by the Hartree–Fock configuration. This capability is illustrated by calculations on molecules containing O–H and O–F bonds, namely OH, FO, H₂O, HOF, and F₂O. To achieve this very high accuracy, it is imperative to account for electron‐correlation effects in a quantitative manner, either by using explicitly correlated two‐particle basis functions (R12 functions) or by extrapolating to the limit of a complete basis. Besides taking into account harmonic zero‐point vibrational energies, it is also necessary to account for anharmonic corrections to the zero‐point vibrational energies, to include the core orbitals into the coupled‐cluster calculations, and to account for spin–orbit corrections and scalar relativistic effects. These additional corrections constitute small but significant contributions in the range of 1–4 kJ mol^?1 to the enthalpies of formation of the aforementioned molecules. The highly accurate coupled‐cluster results, obtained by employing R12 functions and by including various corrections, are compared with standard Kohn–Sham density‐functional calculations as well as with the Gaussian‐2 and complete‐basis‐set model chemistries.     

Reduced–size polarized basis sets for calculations of molecular electric properties. III. Second–row atoms

Reduced–size polarized (ZmPolX) basis sets are developed for the second–row atoms X = Si, P, S, and Cl. The generation of these basis sets follows from a simple physical model of the polarization effect of the external electric field which leads to highly compact polarization functions to be added to the chosen initial basis set. The performance of the ZmPolX sets has been investigated in calculations of molecular dipole moments and polarizabilities. Only a small deterioration of the quality of the calculated molecular electric properties has been found. Simultaneously the size of the present reduced–size ZmPolX basis sets is about one-third smaller than that of the usual polarized (PolX) sets. This reduction considerably widens the range of applications of the ZmPolX sets in calculations of molecular dipole moments, dipole polarizabilities, and related properties.     

Theoretical study of structures of the X<Subscript>2</Subscript>CO and XYCO molecules (X and Y = H,F, or Cl) in the ground and lowest excited triplet electronic states

Systematic calculations of the structures of the H₂CO, F₂CO, Cl₂CO, HClCO, HFCO, and FClCO molecules in the S₀ and T₁ states were performed using the B3LYP and MP2 methods with different AO basis sets and also at the CCSD(T)/cc-pV(T+d)Z level of theory. The saturation of the correlation consistent sequence of basis sets cc-pV(N+d)Z (N = D, T, Q, and 5) and aug-cc-pV(N+d)Z (N = D, T, and Q) was studied. Recommendations for choosing the calculation method are given. The relativistic corrections were estimated. The influence of the number and type of halogen atoms on the geometric parameters of the molecules in the S₀ and T₁ states and the heights of inversion barriers in the T₁ state was investigated. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2625–2635, December, 2005.     

Improved generator coordinate Hartree–Fock method applied to generate Gaussian basis sets for the isoelectronic series of the atoms He to Ne

We have generated Gaussian basis sets (GBSs) for the neutral and the first 20 cations members of the isoelectronic series of each ground state atom from He to Ne with the improved generator coordinate Hartree–Fock (IGCHF) method. For all atomic species studied here, our total energy errors are smaller than those calculated by the original GCHF method using GBSs of the same sizes. The largest difference between our total energy results and those computed with a numerical Hartree–Fock approach is equal to 215 μhartree for Co¹⁷⁺. We also compare the ionization potentials obtained with the IGCHF with the corresponding experimental values. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem 88: 252–262, 2002     

Relativistic Gaussian basis sets for the atoms hydrogen to neon

Gaussian basis sets for use in relativistic molecular calculations are developed for atoms and ions with one to ten electrons. A relativistic radial wavefunction coupled to an angular function of l-symmetry is expanded into a linear combination of spherical Gaussians of the form r ^l exp (–r ²). One set of basis functions is used for all large and small components of the same angular symmetry. The expansion coefficients and the orbital exponents have been determined by minimizing the integral over the weighted square of the deviation between the Dirac or Dirac-Fock radial wavefunctions and their analytical approximations. The basis sets calculated with a weighting function inversely proportional to the radial distance are found to have numerical constants very similar to those of their energy-optimized non-relativistic counterparts. Atomic sets are formed by combining l-subsets. The results of relativistic and non-relativistic calculations based on these sets are analyzed with respect to different criteria, e.g. their ability to reproduce the relativistic total energy contribution and the spin-orbit splitting. Contraction schemes are proposed.Dedicated to Prof. Dr. A. Neckel on occasion of his 60th birthday     

Polarized basis sets and the calculation of infrared intensities from nuclear electric shielding tensors

The idea of the basis set polarization which follows from the known dependence of basis set functions on the perturbation strength is applied to the calculation of the dipole moment derivatives with respect to nuclear displacements. The differentiation of the dipole moment function is replaced by the straightforward evaluation of derivatives of the intramolecular electric field with respect to the external electric field strength. The method and its efficiency are illustrated by a series of calculations of the dipole moment derivatives for the water molecule. Already a polarized basis set of 26 CGTO's derived from the minimal CGTO basis set provides fairly reasonable results.     

大跨桥梁参数识别响应面方法中的近似函数及样本选取

以某大跨斜拉桥实验室物理模型设计参数与动力特性之间复杂的隐式关系为对象,分析响应面模型中近似函数和试验样本对回归模型精度的影响。首先推导多项式和径向基函数响应面模型的建模方法,然后基于斜拉桥三维空间模型的有限元动力分析,比较分析完全二阶多项式与几种径向基函数模型在设计域和扩展设计域内以及噪声污染情况下的回归精度。最后对几种少量样本的试验设计方法和响应面试验设计方法进行了分析。结果表明,径向基函数模型各方面性能优于多项式模型,响应面实验设计方法优于其他方法,少量样本可采用D优化设计,较多样本情况下以中心复合设计较佳。     

YTP高强度调剖剂的研究与应用

分析了影响YTP高强度油田注水井调剖剂成胶时间的因素及其调剖机理.分析表明该调剖剂成胶时间可控、配制简单、方便(现场配制),动用设备少,成本低,对注水井管柱适应性强.室内岩心和64口井的现场试验结果表明:调剖剂对岩心封堵率高,承压能力强,调剖后在相同的注入量条件下,注水压力升高,吸水剖面得到有效调整,在相连通的油井见到明显的增油降水效果.     

Reactivity of haloethanes with hydroxyl radicals: Effects of basis set and correlation energy on reaction energetics

Ab initio calculations on fluoroethane reactions with the hydroxyl radical have been carried out at different levels of theory. The convergence of reaction barriers and reaction enthalpies has been systematically investigated with respect to the size and quality of the basis set and the treatment of correlation energy. The G2 and MP2 barrier heights and reaction enthalpies show the best agreement with the experimental data. The split valence basis sets of triple-zeta quality supplemented by diffuse and polarization functions are necessary to reproduce experimental values for barrier heights and reaction enthalpies at the MP2 level of theory. The full counterpoise correction was used to calculate the basis set superposition error for several standard basis sets, including polarization and diffuse functions. The smallest counterpoise corrections are associated with basis sets that contain polarization and diffuse functions, the diffuse functions being the most effective in reducing BSSE. However, in our case, the uncorrected barrier heights are in better agreement with experimental results than the counterpoise-corrected data. Thus, at the MP2 level of theory, which seems to be dictated for larger electronic systems of chemical interest, the optimal approach is to increase the basis set to the maximum size affordable and to use results without counterpoise corrections for the calculation of reaction barriers. A viable alternative is the use of G2 theory because its results for the barrier heights and reaction enthalpies are in excellent agreement with the experimental data. © 1997 John Wiley & Sons, Inc. J Comput Chem 18: 1190–1199