On the contribution of higher-order excitations to correlation energies: The ground state of the water molecule

Using the results of a configuration interaction calculation reported by Rosenberg and Shavitt, we derive an approximation to the correlation energy which may be associated with the sum to infinite order of all linked diagrams involving singly- and doubly-excited states. This result is compared with that obtained by calculation of the energy through third-order. The fourth-order linked diagrams involving quadruply-excited states are computed. It is shown that there is a considerable degree of cancellation between the fourth-order linked diagram energy terms involving doubly-excited intermediate states only and those which contain quadruply-excited states.     

Revised interpretations of the available x-ray data for B-DNA

Comparisons are made between calculations based on the double-helix and side-by-side models of DNA and data taken from the available x-ray diffraction measurements of the B form of DNA. The SBS model invoked here is an improvement on the one which was published earlier. In our estimation the fibre diffraction patterns do not significantly favour either model. However, the DH model is incompatible with the on-axis form of the cylindrically-averaged Patterson function, whereas the SBS model is compatible (this result is relatively insensitive to appreciable modifications to the SBS structure)—the crucial question is whether the quality of the data is sufficient to make this finding significant. It is shown that the maximum expected effect on the fibre pattern, of exchanging A-T base pairs for G-C base pairs, is less than the probable experimental error.     

Symmetry adaption

The matrix of force constants of a symmetric molecule is reduced to its invariants (nearly diagonal form). For the case of distance dependent potentials these invariants are expressed by the derivations of the potentials and geometric factors. For the purpose of parametrization the inversions of these formulae are derived. The general equilibrium condition and the elimination of the translational and rotational coordinates are discussed. The example of the tetrahedral AB₄ structure is worked out.     

Elastic interaction between force dipoles on a stretchable substrate

The objective of this paper is to study elastic interaction between force dipoles on the surface of a semi-infinite stretchable substrate. The substrate undergoes a uniform, finite pre-stretch, while the additional deformation induced by a force dipole is assumed infinitesimal. By adopting a neo-Hookean constitutive law, the surface Green function for the pre-stretched substrate is obtained. The result is then used to derive the energy of dipolar interaction on the surface. As an application, mutual interaction between two physisorbed molecules is discussed in detail. The dipole moment of a molecule is found from the elementary intermolecular potential, and its dependence on the pre-stretch is established explicitly. Numerical results indicate that pre-stretches can substantially alter the interaction, and thus provide a controllable way to guide the self-assembly of adsorbed molecules on the substrate surface.     

球形主体分子的包结性能及其在制备有机非线性光学材料 中的应用

提出了球形主体分子的设计思想,把具有球形结构的分子柏木醇(1)、马钱子碱(2)、三乙烯二胺(1,4-二氮-二环[2.2.2]辛烷(3)作为主体分子,把酚类化合物,诸如苯酚(4)、邻甲苯酚(5)、间甲苯酚(6)、对甲苯酚(7)、对氯苯酚(8)和对硝基苯酚(11)等作为客体分子,进行了主客体分子相素作用实验,采用粉末X射线衍射、1^HNMR等分析手段确认了包结化合物的形成及主客体分子的摩尔比,摩尔比(H/G)分别为(1)+(4)1:1,(1)+(5)1:1,(1)+(6)1:1,(1)+(7)1:1,(1)+(11)1:2,(2)+(11)1:1,(3)+(4)1:2,(3)+(5)1:3,(3)+(6)1:2,(3)+(7)1:2,(3)+(8)1:2,(3)+(11)1:2,对典型包结化合物的单晶,诸如柏木醇和邻甲苯酚、马钱子碱和对硝基苯酚以及三乙烯二胺和对硝基苯酚,进行了四圆X射线衍射结构分析,结果表明,包结化合物的堆砌结构特征随主体分子的体积大小而改变,从隧道型如(1)+(5)和(2)+(11)转变为夹层型如(3)+(11)。用Nd:YAG激光测试晶体的SHG效应,结果表明,大部分包结物晶体具有非线性光学性质。