Hypercritically enhanced distortion of a phase diagram: The (polystyrene + acetaldehyde) system

We report new experimental evidence of the existence of double critical points in a binary system. Pressure-temperature data on the solubility of (polystyrene + acetaldehyde) were obtained using a low-angle light-scattering technique. Phase diagrams change from an UCST/LCST configuration showing a marked double maxima to an hour-glass shape with a “window of miscibility” as pressure decreases. Successful modeling of these unusual shapes was achieved by using a computation algorithm which incorporates a temperature- and concentration-dependent interaction parameter. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 631–637, 1997     

Alignment of molecules by the Monte Carlo optimization of molecular similarity indices

3D-QSAR uses statistical techniques to correlate calculated structural properties with target properties like biological activity. The comparison of calculated structural properties is dependent upon the relative orientations of molecules in a given data set. Typically molecules are aligned by performing an overlap of common structural units. This “alignment rule” is adequate for a data set, that is closely related structurally, but is far more difficult to apply to either a diverse data set or on the basis of some structural property other than shape, even for sterically similar molecules. In this work we describe a new algorithm for molecular alignment based upon optimization of molecular similarity indices. We show that this Monte Carlo based algorithm is more effective and robust than other optimizers applied previously to the similarity based alignment problem. We show that QSARs derived using the alignments generated by our algorithm are superior to QSARs derived using the more common alignment of fitting of common structural units. © 1997 by John Wiley & Sons, Inc. J Comput Chem 18 : 1344–1353, 1997     

Use of four-factorial design in ion-selective potentiometry for analysis of multi-ionic solutions

Even with small selectivity of electrodes the application of multi-factorial design produces good results for complex ion mixtures. Carrying out serial analyses with this method, the time for the preparation of specimens is shortened and the accuracy of the determination is increased. The electrode selectivity is characterized using regression equations and an interference level diagram. A graphical representation of data is suggested taking into account the dependence of response on the number of interfering cations. Received: 17 June 1997 / Revised: 3 November 1997 / Accepted: 8 November 1997     

Trace element analysis of geological glasses by laser plasma ionization mass spectrometry (LIMS): A comparison with other multielement and microanalytical methods

Laser plasma ionization mass spectrometry (LIMS) is used in our laboratory as an in-situ microanalytical method for the investigation of solids, especially of rocks and minerals. To demonstrate the accuracy of this method we have analyzed homogeneous geological glass samples. The results are compared with data obtained from other analytical techniques. The performance of the LIMS method for geochemical investigations is discussed. Received: 2 December 1996 / Revised: 21 February 1997 / Accepted: 26 February 1997     

Calculation of hydration free energy for a solute with many atomic sites using the RISM theory: A robust and efficient algorithm

We have developed an algorithm for solving the reference interaction site model (RISM) equations for water near a solute molecule with many atomic sites (interaction sites). It is a hybrid of the Newton–Raphson and Picard methods and is judiciously constructed. Various considerations are given so that the computer time can be saved as much as possible. The robustness and high efficiency of the algorithm has been demonstrated for calculating hydration free energies of Met-enkephalin (a peptide with 75 sites) with different conformations. The Jacobian matrix is treated as part of the input data, and it has been found that the same matrix can be used for a considerably large set of different conformations of the solute molecule. © 1997 John Wiley & Sons, Inc. J Comput Chem 18: 1320–1326, 1997     

A reduced-restricted-quasi-Newton–Raphson method for locating and optimizing energy crossing points between two potential energy surfaces

We present a method for the location and optimization of an intersection energy point between two potential energy surfaces. The procedure directly optimizes the excited state energy using a quasi-Newton–Raphson method coupled with a restricted step algorithm. A linear transformation is also used for the solution of the quasi-Newton–Raphson equations. The efficiency of the algorithm is analyzed and demonstrated in some examples. © 1997 John Wiley & Sons, Inc. J Comput Chem 18 :992–1003, 1997     

Multireference perturbation CI I. Extrapolation procedures with CAS or selected zero-order spaces

We discuss the “three class” approximation to full multireference perturbation CI, which greatly reduces the computational effort by restricting the summation of diagrams to determinants belonging to a subspace of the zero-order space. In the framework of the CIPSI algorithm, we propose a new extrapolation procedure allowing recovery of the full “two class” results. The new procedure is applied to complete active spaces (CAS) and to individually selected zero-order spaces. Comparison with a full two class calculation on a CAS shows a reduction of computer time of one or two orders of magnitude in the tests presented here, with an accuracy in the order of 0.1 kcal/mol. Our procedure can thus compete with the CASPT2 algorithm, specifically conceived to deal with CAS. In the case of selected zero-order spaces, the speed-up is less dramatic but the method still retains its advantages. Received: 12 June 1997 / Accepted: 31 July 1997     

Modern strategies for PC-supported spectral analysis of 1D NMR data

 Analysis of high-resolution NMR spectra elucidation has been known for many years. Hard-and software development now permits the implementation of such programs on personal computers. The structural information hidden in complex proton NMR spectra becomes easily accessible by using graphical user interfaces and direct data exchange between programs. A new mode has been implemented in 1D WIN-NMR to support the analysis of multiplet patterns with first order rules. Structure display, direct export mechanisms to the simulation program WIN-DAISY, and an archiving possibility complete the state-of-the-art data analysis. Some practical examples are given. Received: 25 October 1996/Revised: 6 March 1997/Accepted: 10 March 1997     

Constrained optimization in delocalized internal coordinates

Using the recently introduced delocalized internal coordinates, in conjunction with the classical method of Lagrange multipliers, an algorithm for constrained optimization is presented in which the desired constraints do not have to be satisfied in the starting geometry. The method used is related to a previous algorithm by the same author for constrained optimization in Cartesian coordinates [J. Comput. Chem., 13 , 240 (1992)], but is simpler and far more efficient. Any internal (distance or angle/torsion) constraint can be imposed between any atoms in the system whether or not the atoms involved are formally bonded. Imposed constraints can be satisfied exactly. © 1997 John Wiley & Sons, Inc. J Comput Chem 18 :1079–1095, 1997     

The methodology of knowledge acquisition from the collection of IR and UV spectra

An expert system for identification of parts of chemical molecules from IR and UV spectra is described. To develop the system, the intelligent knowledge engineering program environment SCANKEE¹ (elaborated at the Department of Computer Chemistry) was applied. The expert systems for identification of a chemical compound described in the literature use hand-crafted knowledge bases. To eliminate the time-consuming writing of the rules, a module for the automatic creation of rule knowledge bases was developed. The knowledge derives from the collection of molecular spectra of organic compounds and their structural formulae. The algorithm for the automatic generation of the production rules (in the rule knowledge base) is realized in two steps: (i) the creation of the correlation tables and (ii) the generation of the production rules base. Received: 1 July 1997 / Revised: 3 November 1997 / Accepted: 7 November 1997     

Direct sampling time-of-flight mass spectrometers for technological analysis

The practicability of direct sampling time-of-flight mass spectrometers for routine technological analysis is considered. The discussed set incorporates two TOF instruments together covering analysis of solid, liquid, and gas samples without the need for time consuming sample preparation. Both an electron ionization reflectron TOF mass analyzer designed for the analysis of gas and liquid samples and a laser ionization axial electrostatic TOF mass analyzer designed for analysis of solid and powder samples use a single system for data acquisition, collection and processing. These instruments achieve ng/g range sensitivity and mass resolution exceeding 1000. Because of its compact design the system also can be realized as a mobile laboratory for on-site analysis. Prospects for applying the instruments to different technological applications are discussed. Received: 17 July 1997 / Revised: 28 November 1997 / Accepted: 22 December 1997     

Direct sampling time-of-flight mass spectrometers for technological analysis

The practicability of direct sampling time-of-flight mass spectrometers for routine technological analysis is considered. The discussed set incorporates two TOF instruments together covering analysis of solid, liquid, and gas samples without the need for time consuming sample preparation. Both an electron ionization reflectron TOF mass analyzer designed for the analysis of gas and liquid samples and a laser ionization axial electrostatic TOF mass analyzer designed for analysis of solid and powder samples use a single system for data acquisition, collection and processing. These instruments achieve ng/g range sensitivity and mass resolution exceeding 1000. Because of its compact design the system also can be realized as a mobile laboratory for on-site analysis. Prospects for applying the instruments to different technological applications are discussed. Received: 17 July 1997 / Revised: 28 November 1997 / Accepted: 22 December 1997     

True detection limit of rare earth elements in atomic emission analysis with an arc two-jet plasmatron

The “true detection limit” C_L,true was measured by a method proposed by Boumans et al. for 10 prominent lines of La, Ce, Pr, Nd and Sm, the most abundant rare earth elements (REEs) in geological samples. It is demonstrated how spectral interferences can increase of C_L,true. The spectra were excited in an argon arc plasma jet with evaporation powders of five complex natural samples. The data show that there is a significant increase of C_L,true in real samples containing large concentrations of such elements as Ti, Zr, Cr, Nb, Ta and REEs emitting complex spectra. Received: 17 June 1997 / Revised: 20 October 1997 / Accepted: 26 October 1997     

A genetic algorithm for the structural optimization of Morse clusters

This article describes the application of a genetic algorithm for the structural optimization of 19–50-atom clusters bound by medium-range and short-range Morse pair potentials. The GA is found to be efficient and reliable for finding the geometries corresponding to the previously published global minima [Doye JPK, Wales DJ (1997) J Chem Soc Faraday Trans 93: 4233]. Using the genetic algorithm, only a relatively small number of energy evaluations and minimizations are required to find the global minima. By contrast, a simple random search algorithm often cannot find the global minima of the larger clusters, even after many thousands of searches. Received: 27 October 1999 / Accepted: 7 December 1999 / Published online: 19 April 2000     

Variational transition state theory without the minimum-energy path

In this paper we propose a method for carrying out variational transition state theory calculations without first obtaining a converged minimum-energy path (MEP). We illustrate the method in two ways, first of all by employing an unconverged MEP and secondly by using a dynamically optimized distinguished reaction path. Preliminary tests of the algorithm for the reactions OH+H₂→H₂O+H and C₂H₅→C₂H₄+H are very encouraging. Received: 22 January 1997 / Accepted: 11 March 1997     

Numerical comparisons of three recently proposed algorithms in the protein folding problem

We numerically compare the effectiveness of three recently proposed algorithms, multicanonical algorithm, simulations in a 1/k-sampling, and simulated tempering, for the protein folding problem. We perform simulations with high statistics for one of the simplest peptides, met-enkephalin. While the performances of all three approaches is much better than traditional methods, we find that the differences among the three are only marginal. © 1997 by John Wiley & Sons, Inc. J Comput Chem 18: 920–933, 1997     

Assessing the deposition and remobilisation behaviour of metals between river water and river sediment using partial least squares regression

Partial least squares regression (PLS) as a method for multivariate data analysis has been applied to environmental data of the German rivers Saale, Ilm and Unstrut. Main aspects of the study are to describe the relationships of the distribution of metals between river water and river sediment using PLS. A simulation of the distribution of metals between the liquid and solid phase by variation of some parameters (e.g. conductivity, DOC, dissolved oxygen, pH, phosphate and suspended matter) is presented and compared with experimental results. Received: 15 July 1997 / Revised: 6 November 1997 / Accepted: 7 November 1997     

A scalable divide-and-conquer algorithm combining coarse and fine-grain parallelization

We describe an efficient algorithm for carrying out a “divide-and-conquer” fit of a molecule's electronic density on massively parallel computers. Near linear speedups are achieved with up to 48 processors on a Cray T3E, and our results indicate that similar efficiencies could be attained on an even greater number of processors. To achieve optimum efficiency, the algorithm combines coarse and fine-grain parallelization and adapts itself to the existing ratio of processors to subsystems. The subsystems employed in our divide-and-conquer approach can also be made smaller or bigger, depending on the number of processors available. This allows us to further reduce the wallclock time and improve the method's overall efficiency. The strategies implemented in this paper can be extended to any other divide-and-conquer method used within an ab initio, density functional, or semi-empirical quantum mechanical program. Received: 15 September 1997 / Accepted: 21 January 1998     

Immuno-affinity columns versus conventional clean-up: a method-comparison study for the determination of zearalenone in corn

The efficiency of a modern analytical method employing immuno-affinity columns (IACs) is compared to a well established traditional technique with respect to the determination of zearalenone (ZON) in corn in the μg/kg range. Despite of a constant error of about 4 μg/kg in the examined working range of 10–200 μg/kg, analytical data obtained from the analysis of spiked and naturally contaminated samples showed good correspondence for the compared methods. The performance characteristics of immuno-affinity-chromatography as a new clean-up technique for the determination of ZON in corn is reported for the first time and compared to a conventional clean-up procedure Received: 25 March 1997 / Revised: 5 May 1997 / Accepted: 12 May 1997     

Modification of Guest and Saunders open shell SCF equations to exclude BSSE from molecular interaction calculations

The self-consistent field (SCF) for molecularinteractions algorithm, particularly devised to compute intermolecular interactions, is extended to the case in which one of the two interacting fragments is an open shell system. The method excludes the basis set superposition error in an a priori fashion. To preserve the simplicity of the standard SCF procedure, Guest and Saunders equations concerning the open shell fragment are modified at the cost of a negligible complication with respect to the usual algorithm. Received: 27 May 1997 / Accepted: 29 May 1998 / Published online: 18 September 1998