Derivation of class II force fields. VIII. Derivation of a general quantum mechanical force field for organic compounds

A class II valence force field covering a broad range of organic molecules has been derived employing ab initio quantum mechanical "observables." The procedure includes selecting representative molecules and molecular structures, and systematically sampling their energy surfaces as described by energies and energy first and second derivatives with respect to molecular deformations. In this article the procedure for fitting the force field parameters to these energies and energy derivatives is briefly reviewed. The application of the methodology to the derivation of a class II quantum mechanical force field (QMFF) for 32 organic functional groups is then described. A training set of 400 molecules spanning the 32 functional groups was used to parameterize the force field. The molecular families comprising the functional groups and, within each family, the torsional angles used to sample different conformers, are described. The number of stationary points (equilibria and transition states) for these molecules is given for each functional group. This set contains 1324 stationary structures, with 718 minimum energy structures and 606 transition states. The quality of the fit to the quantum data is gauged based on the deviations between the ab initio and force field energies and energy derivatives. The accuracy with which the QMFF reproduces the ab initio molecular bond lengths, bond angles, torsional angles, vibrational frequencies, and conformational energies is then given for each functional group. Consistently good accuracy is found for these computed properties for the various types of molecules. This demonstrates that the methodology is broadly applicable for the derivation of force field parameters across widely differing types of molecular structures. Copyright 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1782-1800, 2001     

Synthesis of alpha-fluorosulfonamides by electrophilic fluorination

Alpha-fluorosulfonamides were prepared by electrophilic fluorination of tertiary sulfonamides using N-fluorobenzenesulfonimide as fluorinating agent and utilizing the dimethoxybenzyl group (DMB) as a new sulfonamide protecting group. Removal of the DMB group with TFA/CH(2)Cl(2) gave primary and secondary alpha-fluorosulfonamides.     

Structural analysis of phosphatidylcholines by post-source decay matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

The utility of post-source decay (PSD) matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) was investigated for the structural analysis of phosphatidylcholine (PC). PC did not produce detectable negative molecular ion from MALDI, but positive ions were observed as both [PC+H](+) and [PC+Na](+). The PSD spectra of the protonated PC species contained only one fragment corresponding to the head group (m/z 184), while the sodiated precursors produced many fragment ions, including those derived from the loss of fatty acids. The loss of fatty acid from the C-1 position (sn-1) of the glycerol backbone was favored over the loss of fatty acid from the C-2 position (sn-2). Ions emanating from the fragmentation of the head group (phosphocholine) included [PC+Na-59](+), [PC+Na-183](+) and [PC+Na-205](+), which corresponded to the loss of trimethylamine (TMA), non-sodiated choline phosphate and sodiated choline phosphate, respectively. Other fragments reflecting the structure of the head group were observed at m/z 183, 146 and 86. The difference in the fragmentation patterns for the PSD of [PC+Na](+) compared to [PC+H](+) is attributed to difference in the binding of Na(+) and H(+). While the proton binds to a negatively charged oxygen of the phosphate group, the sodium ion can be associated with several regions of the PC molecule. Hence, in the sodiated PC, intermolecular interaction of the negatively charged oxygen of the phosphate group, along with sodium association at multiple sites, can lead to a complex and characteristic ion fragmentation pattern. The preferential loss of sn-1 fatty acid group could be explained by the formation of an energetically favorable six-member ring intermediate, as apposed to the five-member ring intermediate formed prior to the loss of sn-2 fatty acid group.     

Gamow-Teller beta decay of the very neutron-deficientN=50 nuclide98Cd

For the first time, detailed decay-spectroscopic investigations were performed for the very neutron-deficientN=50 nuclide⁹⁸Cd. The⁹⁸Cd activity was produced in spallation reactions between 600 MeV protons and a natural tin target, yielding a⁹⁸Cd beam intensity of 10 to 60 atoms/s at the collector of the ISOLDE massseparator. By means of-ray and conversion-electron spectroscopy, 19 transitions were found to follow the ⁺/EC decay⁹⁸Cd⁹⁸Ag. The transitions at 61 and 107 keV were shown to beM1(+E2) andE2, respectively, and the⁹⁸Cd half-life was measured as 9.2±0.3 s. TheQ _EC value of⁹⁸Cd is determined semiempirically and is compared to model predictions together with the measuredQ _EC values of the neighbouring cadmium isotopes^100,102Cd and theN=50 isotones⁹²Mo,⁹⁴Ru, and⁹⁶Pd, taken from the literature. The newly established decay scheme of⁹⁸Cd includes 9 excited states of⁹⁸Ag. Four states at 1691, 1861, 2164, and 2544 keV are directly fed by 0⁺ 1⁺ Gamow-Teller beta transitions with a summed strength of 3.5 _–0.7 ^+0.8 . This value corresponds to 25±5% of the strength predicted for the GT transformation of a g_9/2 proton (in⁹⁸Cd) into a g_7/2 neutron (in⁹⁸Ag) by the extreme single-particle shell model. The GT-strength splitting and quenching, observed for⁹⁸Cd, are compared with the corresponding data for lighter even-even N=50 isotones, and are discussed with reference to the predictions of more sophisticated nuclear models. We find that only in some cases it is possible to explain qualitatively the observed GT strength distribution and its total magnitude without renormalizing the free-neutron value of the axial-vector coupling constant.Dedicated to Prof. P. Armbruster on the occasion of his 60th birthday