Gaussian basis sets of quadruple zeta valence quality for Rb-Rn are presented, as well as bases of split valence and triple zeta valence quality for H-Rn. The latter were obtained by (partly) modifying bases developed previously. A large set of more than 300 molecules representing (nearly) all elements-except lanthanides-in their common oxidation states was used to assess the quality of the bases all across the periodic table. Quantities investigated were atomization energies, dipole moments and structure parameters for Hartree-Fock, density functional theory and correlated methods, for which we had chosen Moller-Plesset perturbation theory as an example. Finally recommendations are given which type of basis set is used best for a certain level of theory and a desired quality of results.

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy

CHARMM (Chemistry at HARvard Macromolecular Mechanics) is a highly flexible computer program which uses empirical energy functions to model macromolecular systems. The program can read or model build structures, energy minimize them by first- or second-derivative techniques, perform a normal mode or molecular dynamics simulation, and analyze the structural, equilibrium, and dynamic properties determined in these calculations. The operations that CHARMM can perform are described, and some implementation details are given. A set of parameters for the empirical energy function and a sample run are included.

CHARMM: A program for macromolecular energy, minimization, and dynamics calculations

New protein parameters are reported for the all-atom empirical energy function in the CHARMM program. The parameter evaluation was based on a self-consistent approach designed to achieve a balance between the internal (bonding) and interaction (nonbonding) terms of the force field and among the solvent−solvent, solvent−solute, and solute−solute interactions. Optimization of the internal parameters used experimental gas-phase geometries, vibrational spectra, and torsional energy surfaces supplemented with ab initio results. The peptide backbone bonding parameters were optimized with respect to data for N-methylacetamide and the alanine dipeptide. The interaction parameters, particularly the atomic charges, were determined by fitting ab initio interaction energies and geometries of complexes between water and model compounds that represented the backbone and the various side chains. In addition, dipole moments, experimental heats and free energies of vaporization, solvation and sublimation, molecular volume...

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All-atom empirical potential for molecular modeling and dynamics studies of proteins.

We present the theoretical and technical foundations of the Amsterdam Density Functional (ADF) program with a survey of the characteristics of the code (numerical integration, density fitting for the Coulomb potential, and STO basis functions). Recent developments enhance the efficiency of ADF (e.g., parallelization, near order-N scaling, QM/MM) and its functionality (e.g., NMR chemical shifts, COSMO solvent effects, ZORA relativistic method, excitation energies, frequency-dependent (hyper)polarizabilities, atomic VDD charges). In the Applications section we discuss the physical model of the electronic structure and the chemical bond, i.e., the Kohn–Sham molecular orbital (MO) theory, and illustrate the power of the Kohn–Sham MO model in conjunction with the ADF-typical fragment approach to quantitatively understand and predict chemical phenomena. We review the “Activation-strain TS interaction” (ATS) model of chemical reactivity as a conceptual framework for understanding how activation barriers of various types of (competing) reaction mechanisms arise and how they may be controlled, for example, in organic chemistry or homogeneous catalysis. Finally, we include a brief discussion of exemplary applications in the field of biochemistry (structure and bonding of DNA) and of time-dependent density functional theory (TDDFT) to indicate how this development further reinforces the ADF tools for the analysis of chemical phenomena. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 931–967, 2001

Chemistry with ADF

A method of ‘‘natural population analysis’’ has been developed to calculate atomic charges and orbital populations of molecular wave functions in general atomic orbital basis sets. The natural analysis is an alternative to conventional Mulliken population analysis, and seems to exhibit improved numerical stability and to better describe the electron distribution in compounds of high ionic character, such as those containing metal atoms. We calculated ab initio SCF‐MO wave functions for compounds of type CH3X and LiX (X=F, OH, NH2, CH3, BH2, BeH, Li, H) in a variety of basis sets to illustrate the generality of the method, and to compare the natural populations with results of Mulliken analysis, density integration, and empirical measures of ionic character. Natural populations are found to give a satisfactory description of these molecules, providing a unified treatment of covalent and extreme ionic limits at modest computational cost.

Natural population analysis

The electron affinity of LiBO2 and the structure of its negative ion, LiBO−2

The lithium salts of the two title dianions have been synthesised and investigated by 1H and 13C n.m.r. spectroscopy. Whereas the dibenzylidenemethylenemethane dianion salt exists exclusively in the exo,exo conformation, its oxa-analogue is a mixture of two isomers, exo,endo and a symmetrical form, probably exo,exo. The benzyl α,β-CC bond rotation barrier in the ketone dianion salt in THF is 10.8 ± 0.5 kcal mol–1. The phenyl rotation barrier in the hydrocarbon dianion salt is similar (10.9 kcal mol–1), as are the charge distributions in the benzylidene groups of the two dianions.

Y-Conjugated dianions: a comparison between the 1,1-dibenzylethylene and diphenylacetone-derived dianions

Ein fünfatomiges Molekül, das in einem einzigen Schritt über chirale Übergangszustände enantiomerisiert

Theoretische Studien zu Struktur, Aromatizität und magnetischen Eigenschaften von 1,2‐Didehydrobenzol

The most stable structure of CB2H3−, as established computationally, is the aromatic diboracyclopropenyl (diboriranyl) anion (5), while open-chainC2v, isomer H2BCBH (7) is only 3 kcal/mol higher in energy at the QCISD(T)/6-311 +G**//MP2/6-31+G*+ZPE (HF/6-31 +G*). The 47-kcal/mol barrier between cyclic,5, and open-chain,7, structures suggests that both of them may be observed. The aromatic stabilization energy of the diboriranyl anion (18 kcal/mol) is half the value in the isoelectronic cyclopropenium ion, C3H3+. The computed, by IGLO method (5a), and experimental (6a) chemical shifts,δ(13C) andδ(11B), agree within 4 ppm range. The theoretical vibrational frequencies of the most stable isomers,5 and7, are presented for experimental verification of these species.

Paul von Ragué Schleyer

Papers

The electron affinity of LiBO2 and the structure of its negative ion, LiBO−2

Y-Conjugated dianions: a comparison between the 1,1-dibenzylethylene and diphenylacetone-derived dianions

Ein fünfatomiges Molekül, das in einem einzigen Schritt über chirale Übergangszustände enantiomerisiert

Theoretische Studien zu Struktur, Aromatizität und magnetischen Eigenschaften von 1,2‐Didehydrobenzol

The aromatic diboracyclopropenyl (diboriranyl) anion; CB2H3−: An ab initio study