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41.
Fused-sphere surfaces can be used to mimic a molecular boundary associated with a constant value of the electron density. The simplest of such fused-sphere models are constructed by using the atomic radii for the spherical isodensity surfaces of individual atoms. In this work, we discuss the extension of this model to molecules containing atoms beyond the second row. In these many- electron systems, the computation of electron densities is usually simplified by adopting a pseudopotential (or effective-core potential) approach. Here, we discuss the performance of large- and small-core pseudo-potential calculations as a tool to derive atomic radii. Our results provide an optimum set of variable radii that can be used to build fused-sphere surfaces. This continuum of surfaces provides a simple approximation to the low-electron-density regions around molecules with heavy atoms. 相似文献
42.
R. Centoducatte E. P. Muniz F. E. Jorge M. T. Barreto 《Journal of Molecular Structure》2004,680(1-3):143-147
The molecular improved generator coordinate Hartree–Fock (MIGCHF) method is used to generate accurate basis sets of primitive Gaussian-type functions for the H2O molecule. Sequences of increasing size atom centered basis sets are employed to explore the accuracy that can be achieved with this method. Using the O(24s14p8d5f2g1h);H(22s9p5d2f1g) basis set, the HF and second-order electron correlation energies of the H2O ground state at the experimental geometry are computed as −76.0674680 and −0.3491935 hartree, respectively. The HF energy is in error by 20 μhartree and the second-order correlation energy corresponds to 96.5% of an estimate of the limiting value. The relevance of the present calculations is to show the accuracy that can be achieved in studies of small polyatomic molecules with the MIGCHF method. 相似文献
43.
P.A. Fantin P.L. Barbieri A. Canal Neto F.E. Jorge 《Journal of Molecular Structure》2007,810(1-3):103-111
44.
45.
Daniel M. Chipman 《Theoretical chemistry accounts》1989,76(2):73-84
Summary The suitability of Gaussian basis sets for ab initio calculation of Fermi contact spin densities is established by application to the prototype first-row atoms B-F having open shell p electrons. Small multiconfiguration self-consistent-field wave functions are used to describe relevant spin and orbital polarization effects. Basis sets are evaluated by comparing the results to highly precise numerical grid calculations previously carried out with the same wave function models. It is found that modest contracted Gaussian basis sets developed primarily for Hartree-Fock calculations can give semiquantitative results if augmented by diffuse functions and if further uncontracted in the outer core-inner valence region. 相似文献
46.
47.
De Jong GT Geerke DP Diefenbach A Solà M Bickelhaupt FM 《Journal of computational chemistry》2005,26(10):1006-1020
We have computed a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the ethane C-C bond to the palladium atom and have used this to evaluate the performance of 24 popular density functionals, covering LDA, GGA, meta-GGA, and hybrid density functionals, for describing this reaction. The ab initio benchmark is obtained by exploring the PES using a hierarchical series of ab initio methods [HF, MP2, CCSD, CCSD(T)] in combination with a hierarchical series of five Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Our best estimate of kinetic and thermodynamic parameters is -10.8 (-11.3) kcal/mol for the formation of the reactant complex, 19.4 (17.1) kcal/mol for the activation energy relative to the separate reactants, and -4.5 (-6.8) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). Our work highlights the importance of sufficient higher angular momentum polarization functions for correctly describing metal-d-electron correlation. Best overall agreement with our ab initio benchmark is obtained by functionals from all three categories, GGA, meta-GGA, and hybrid DFT, with mean absolute errors of 1.5 to 2.5 kcal/mol and errors in activation energies ranging from -0.2 to -3.2 kcal/mol. Interestingly, the well-known BLYP functional compares very reasonably with a slight underestimation of the overall barrier by -0.9 kcal/mol. For comparison, with B3LYP we arrive at an overestimation of the overall barrier by 5.8 kcal/mol. On the other hand, B3LYP performs excellently for the central barrier (i.e., relative to the reactant complex) which it underestimates by only -0.1 kcal/mol. 相似文献
48.
In this article, we apply a novel time‐dependent discrete variable representation (TDDVR) method proposed by Barkakaty and Adhikari to investigate tunneling through an Eckart barrier. This semi‐classical method is theoretically rigorous and straightforward to implement. Among the TDDVR formulations, this report presents the first derivation of a rigorous form of quantum force (QF) for the present perspective. The validity of this semi‐classical approach is demanded based on the excellent agreement of the tunneling probability with the corresponding quantum results. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004 相似文献
49.
50.
We propose an algorithm for the computation ofL
1 (LAD) smoothing splines in the spacesW
M
(D), with
. We assume one is given data of the formy
i
=(f(t
i
) +
i
, i=1,...,N with {itti}
i=1
N D
, the
i
are errors withE(
i
)=0, andf is assumed to be inW
M
. The LAD smoothing spline, for fixed smoothing parameter0, is defined as the solution,s
, of the optimization problem
(1/N)
i=1
N
¦y
i
–g(t
i
¦+J
M
(g), whereJ
M
(g) is the seminorm consisting of the sum of the squaredL
2 norms of theMth partial derivatives ofg. Such an LAD smoothing spline,s
, would be expected to give robust smoothed estimates off in situations where the
i
are from a distribution with heavy tails. The solution to such a problem is a thin plate spline of known form. An algorithm for computings
is given which is based on considering a sequence of quadratic programming problems whose structure is guided by the optimality conditions for the above convex minimization problem, and which are solved readily, if a good initial point is available. The data driven selection of the smoothing parameter is achieved by minimizing aCV() score of the form
.The combined LAD-CV smoothing spline algorithm is a continuation scheme in 0 taken on the above SQPs parametrized in, with the optimal smoothing parameter taken to be that value of at which theCV() score first begins to increase. The feasibility of constructing the LAD-CV smoothing spline is illustrated by an application to a problem in environment data interpretation. 相似文献