Showing papers by "Ernest R. Davidson published in 1986"

Basis Set Selection for Molecular Calculations

Abstract: The quantum chemistry literature containa references to a plethora of basis seta, currently numbering almost 100. While professional quantum chemists might become familiar with several dozen of these in a lifetime of calculations, the OCeasionaJ user of ab initio programs probably wishes to ignore all but the two or three sets which, through habitual use, have become personal favorites. Unfortunately, this attitude has its drawbacks. Intelligent reading of the literature requires a t least a cursory knowledge of the limitations of other basis sets. Information conceming the likely aceuracy of a specific basis for a particular property is essential in order to judge the adequacy of the computational method and, hence, the soundness of the results. Occasionally, for reasons of economy or computational feasibility, a basii set is selected for which the computed results are nearly without significance. In light of the large number of publications reporting new basis sets or detailing the performance of existing sets the task of remaining informed has become very diffteult for experts and nonexperts alike. The existence of such a vast multitude of basis sets is attributable, a t least in part, to the difficulty of finding a single set of functions which is flexible enough to produce 'good" results over a wide range of molecular geometries and is still small enough to leave the problem computationally tractible and economically within reason. The driving force behind much of the research effort in small basis sets is the fact that the computer time required for some parts of an ab initio calculation is very strongly dependent on the number of basis functions. For example, the integral evaluation goes as the fourth power of the number of Gaussian primitives. Fortunately this is the only step which explicitly depends on the number of primitives. All subsequent steps depend on the number of contracted functions formed from the primitives. The concept of primitive and contracted functions will be discussed later. Consider a collection of K identical atoms, each with n doubly occupied orbitals and N unoccupied (or virtual) orbitals. The SCF step increases as (n + N'K', while the full transformation of the integrals over the original basis functions to integrals over molecular orbitals goes as (n + N5P. Methods to account for correlation effects vary greatly. Only a few of the popular ones will be considered here. Second order Moller-Plesset (MP2) perturbation theory goes as n2NX4 but still requires an nN4F integral transformation. MP3 goes as n2N4P, while a Hartree-Fock singles and doubles CI will have n2WK4 configurations, (n2NW')' hamiltonian matrix elements of which n2N4P will be nonzero. Pople and co-workers' have proposed

Rotationally resolved laser photoelectron spectra of gas-phase NO: rotational propensity rules in photoionization

Abstract: Rotationally resolved laser photoelectron spectra were recorded by exciting specific rovibronic levels in the A/sup 2/..sigma../sup +/, C/sup 2/II, and D/sup 2/..sigma../sup +/ Rydberg states of NO, to study the rotational propensity rules in photoionization. The data for the A and C states are in excellent agreement with theoretical calculations of Bonham et al. and the model of Pratt et al. The D state spectra show, in addition to the expected propensities, a strong ..delta..N = 0 peak. On the basis of theoretical calculations they infer that the continuum wave excited by ionizing NO from its D state cannot be adequately described by a single l quantum number.

Neon matrix ESR and CI theoretical investigation of 10BF+ and 11BF+: Photoionization of BF from reactive laser sputtering and high temperature sources

Abstract: The 11BF+ and 10BF+ radical cations have been generated and trapped in neon matrices at 4 K using the combined techniques of pulsed reactive laser sputtering and photoionization at 16.8 eV. An independent high temperature source of BF(g) in conjunction with photoionization was also employed and a comparison between these two different generation methods reveals no significant differences in their ESR spectra. The magnetic parameters for 11BF+ measured in neon matrices are g∥=2.0012(3), g⊥=2.0004(3), (11B) A∥=1784(1), and A⊥=1727(1) MHz, (19F)A∥=410(1), and A⊥=152(1) MHz. Extensive ab initio theoretical calculations have been conducted for BF+ and the nuclear hyperfine properties obtained from various types of CI wave functions show excellent agreement with the experimental measurements. Valence orbital occupancies obtained from a Mulliken‐type population analysis performed on the CI wave functions are compared with the conventional free atom comparison method for obtaining electronic structure information...