Improved semiempirical heats of formation through the use of bond and group equivalents

Deficiencies in energetics obtained using the common semiempirical methods, AM1, PM3, and MNDO, may partly be traced to the use of pseudoatomic equivalents for conversion of molecular energies to heats of formation at 298 K. We present an alternative scheme based on the use of bond and group equivalents. Values for the 61 bond and group equivalents necessary for treatment of molecules containing the common organic elements, hydrogen, carbon, nitrogen, and oxygen have been derived. For a set of 583 neutral, closed-shell molecules mean absolute errors in AM1, PM3, and MNDO heats of formation are reduced from 6.6, 4.2, and 8.2 kcal/mol to 2.3, 2.2, and 3.0 kcal/mol, respectively. Several systematic problems are overcome in the present scheme including relative stabilities of branched hydrocarbons, energetics of conjugated systems, heats of formation of long chain hydrocarbons, and enthalpies of molecules containing multiple heteroatoms. Although the approach is restricted to molecules with well-defined functional groups, the equivalents are easy to incorporate and are chemically relevant. This revised procedure allows semiempirical methods to be used for far more reliable evaluations of heats of reactions. Estimates are made of the errors inherent in these semiempirical formalisms, arising from integral approximations and the neglect of explicit treatment of electron correlation effects, while excluding those from inadequate parameterization.     

Tight Distance-Regular Graphs

We consider a distance-regular graph with diameter d 3 and eigenvalues k = ₀ > ₁ > ... > _d . We show the intersection numbers a ₁, b ₁ satisfy

Continuous-time mean-variance portfolios: a comparison

In this article, we present and compare three mean-variance optimal portfolio approaches in a continuous-time market setting. These methods are the L ²-projection as presented in Schweizer [M. Schweizer, Approximation of random variables by stochastic integrals, Ann. Prob. 22 (1995), pp. 1536–1575], the Lagrangian function approach of Korn and Trautmann [R. Korn and S. Trautmann, Continuous-time portfolio optimization under terminal wealth constraints, ZOR-Math. Methods Oper. Res. 42 (1995), pp. 69–92] and the direct deterministic approach of Lindberg [C. Lindberg, Portfolio optimization when expected stock returns are determined by exposure to risk, Bernoulli 15 (2009), pp. 464–474]. As the underlying model, we choose the recent innovative market parameterization introduced by Lindberg (2009) that has the particular aim to overcome the estimation problems of the stock price drift parameters. We derive some new results for the Lagrangian function approach, in particular explicit representations for the optimal portfolio process. Further, we compare the different optimization frameworks in detail and highlight their attractive and not so attractive features by numerical examples.     

Arc Length Estimation and the Convergence of Polynomial Curve Interpolation

When fitting parametric polynomial curves to sequences of points or derivatives we have to choose suitable parameter values at the interpolation points. This paper investigates the effect of the parameterization on the approximation order of the interpolation. We show that chord length parameter values yield full approximation order when the polynomial degree is at most three. We obtain full approximation order for arbitrary degree by developing an algorithm which generates more and more accurate approximations to arc length: the lengths of the segments of an interpolant of one degree provide parameter intervals for interpolants of degree two higher. The algorithm can also be used to estimate the length of a curve and its arc-length derivatives. AMS subject classification (2000) 65D05, 65D10     

Covariance Partition Priors: A Bayesian Approach to Simultaneous Covariance Estimation for Longitudinal Data

The estimation of the covariance matrix is a key concern in the analysis of longitudinal data. When data consist of multiple groups, it is often assumed the covariance matrices are either equal across groups or are completely distinct. We seek methodology to allow borrowing of strength across potentially similar groups to improve estimation. To that end, we introduce a covariance partition prior that proposes a partition of the groups at each measurement time. Groups in the same set of the partition share dependence parameters for the distribution of the current measurement given the preceding ones, and the sequence of partitions is modeled as a Markov chain to encourage similar structure at nearby measurement times. This approach additionally encourages a lower-dimensional structure of the covariance matrices by shrinking the parameters of the Cholesky decomposition toward zero. We demonstrate the performance of our model through two simulation studies and the analysis of data from a depression study. This article includes Supplementary Materials available online.     

A Flexible Parameterization for Baseline Mean Degree in Multiple-Network ERGMs

The conventional exponential family random graph model (ERGM) parameterization leads to a baseline density that is constant in graph order (i.e., number of nodes); this is potentially problematic when modeling multiple networks of varying order. Prior work has suggested a simple alternative that results in constant expected mean degree. Here, we extend this approach by suggesting another alternative parameterization that allows for flexible modeling of scenarios in which baseline expected degree scales as an arbitrary power of order. This parameterization is easily implemented by the inclusion of an edge count/log order statistic along with the traditional edge count statistic in the model specification.     

基于RMC的微观截面参数化北大核心CSCD

为了进行堆芯计算,需要通过组件计算提前构建少群截面参数库。传统确定论的组件截面参数化方法针对宏观截面进行截面参数化,但这种方式不仅需要考虑多种物理状态参数,而且需要考虑历史效应对截面的影响。提出了基于核素微观截面的蒙卡程序参数化方法,该方法可以消除燃耗历史的影响,且考虑的物理状态仅为燃耗深度以及材料温度。利用蒙卡程序产生组件截面参数库耦合堆芯程序进行堆芯计算,首先用蒙卡程序同时统计对应状态点下的核素密度以及核素少群微观截面,再利用核素微观截面进而获得宏观截面进行后续堆芯计算。为了验证方法正确性,构造了一个自定义的压水堆模型,计算结果与连续能量蒙卡计算结果符合良好。