Accurate calculation of the scattering length for the cooling of hydrogen atoms by lithium atoms

An improved ab initio calculation has been performed for the potential for the LiH a ³Σ⁺ state, using two very large basis sets. The Basis Set Superposition Error (BSSE) correction has been determined for both basis sets and the non-Born-Oppenheimer correction estimated to be negligible. The best potential is approximately 10% deeper than the previous estimate. Vibrational energies and scattering lengths have been calculated for ^6,7LiH(D) with both potentials, with and without the BSSE correction, and also with an estimated potential expected to bracket the true potential. The ⁷LiH scattering length is estimated to be (45 ± 4)a₀ and hence the low-energy cross-section in the best a ³Σ⁺ potential is about half that calculated previously. Enhanced cooling by ⁷Li of trapped H atoms remains feasible. Received 30 April 2001     

Theoretically calculated rovibronic transition spectra of KRb

Spectroscopic properties of all the electronic states of KRb dissociating into 4s(K) + 5s(Rb), 4s(K) + 5p(Rb), 4p(K) + 5s(Rb), and 4s(K) + 4d(Rb) and some higher-lying excited states are studied with ab initio calculations. Spectroscopic constants, dipole moments, and the nature of the electronic wave functions for these states are reported. Intensities for the singlet-singlet and triplet-triplet transitions are theoretically calculated from the potential energy curves and the transition dipole moments. © 1996 John Wiley & Sons, Inc.     

Systematic Study of Selected Diagonalization Methods for Configuration Interaction Matrices

Several modifications to the Davidson algorithm are systematically explored to establish their performance for an assortment of configuration interaction (CI) computations. The combination of a generalized Davidson method, a periodic two‐vector subspace collapse, and a blocked Davidson approach for multiple roots is determined to retain the convergence characteristics of the full subspace method. This approach permits the efficient computation of wave functions for large‐scale CI matrices by eliminating the need to ever store more than three expansion vectors ( b _i) and associated matrix‐vector products ( σ _i), thereby dramatically reducing the I/O requirements relative to the full subspace scheme. The minimal‐storage, single‐vector method of Olsen is found to be a reasonable alternative for obtaining energies of well‐behaved systems to within μE_h accuracy, although it typically requires around 50% more iterations and at times is too inefficient to yield high accuracy (ca. 10^?10 E_h) for very large CI problems. Several approximations to the diagonal elements of the CI Hamiltonian matrix are found to allow simple on‐the‐fly computation of the preconditioning matrix, to maintain the spin symmetry of the determinant‐based wave function, and to preserve the convergence characteristics of the diagonalization procedure. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1574–1589, 2001     

Hydrostannylation of phosphaalkenes [1]

Hydrostannylation reactions of the phosphaalkenes 9,11, and 21 with the triorganotin hydrides 1 proceed by different routes. Whereas the trior-ganotin hydrides 1a,b undergo regioselective 1,2-addition to the P/C double bond of the P-aminophosphaalkene 9 to furnish the 2-stannylphosphanes 17a,b, the 1,2-addition products to the P-halophosphaalkenes 11 and 21 can only be postulated as the reactive intermediates 20 and 23, respectively. The reactions of 11 with 1a,b proceed with cleavage of the triorganotin halide via the diphosphene 15 to furnish the cyclophosphanes 18 and 19. On the other hand, the hydrostannylation reactions of the phosphaalkene 21 are not selective, and the 1,3-diphosphetane 22 is isolated as one of the reaction products. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:453–460, 1998     

Charge transfer and mixed-valence behavior in phtalocyanine-dimer cations

Phtalocyanine compounds deserved a considerable interest in recent times, particularly because of their possible use in the field of nanoelectronics. In particular, the charge mobility (of both electrons and holes) in phtalocyanine stacked arrangements has been recently extensively investigated. The present work focuses on the study of the hole-transfer mechanism between two phtalocyanine monomers. For an interdisk distance larger than 4.5 bohrs, the eclipsed dimer exhibits a mixed-valence behavior, with a saddle point transition state separating two equivalent minima. This behavior, however, is strongly dependent on the relative angle between the disks. In particular, the mixed-valence character of the compound is strongly enhanced for arrangements that are far from the eclipsed geometry. Moreover, for values of the angle close to π/8 and 3π/8, the ground and excited transition states have exactly the same energy, thus implying the presence of a conical intersection. These results can have deep implication in the charge transfer along phtalocyanine chains.     

Ground state of the quasi-1D compound BaVS3 resolved by resonant magnetic x-ray scattering

Resonant magnetic x-ray scattering near the vanadium L2,3-absorption edges has been used to investigate the low temperature magnetic structure of high quality BaVS3 single crystals. Below T(N)=31 K, the strong resonance revealed a triple-incommensurate magnetic ordering at the wave vector (0.226 0.226 ξ) in hexagonal notation, with ξ=0.033. The azimuthal-angle dependence of the scattering signal and time-dependent density functional theory simulations indicate an antiferromagnetic order within the ab plane with the spins polarized along a in the monoclinic structure.     

Separable subgroups of mapping class groups

We investigate separability questions for the mapping class group of a surface. While this group is not subgroup separable in general, we prove a large family of interesting subgroups are separable. This includes many classically studied subgroups such as solvable subgroups, Heegaard and Handlebody groups, geometric subgroups, and all the terms in the Johnson filtration.