8 resultados para Distributed Calculations
em Bucknell University Digital Commons - Pensilvania - USA
Resumo:
Acid dissociation constants, or pKa values, are essential for understanding many fundamental reactions in chemistry. These values reveal the deprotonation state of a molecule in a particular solvent. There is great interest in using theoretical methods to calculate the pKa values for many different types of molecules. These include molecules that have not been synthesized, those for which experimental pKa determinations are difficult, and for larger molecules where the local environment changes the usual pKa values, such as for certain amino acids that are part of a larger polypeptide chain. Chemical accuracy in pKa calculations is difficult to achieve, because an error of 1.36 kcal/mol in the change of free energy for deprotonation in solvent results in an error of 1 pKa unit. In this review the most valuable methods for determining accurate pKa values in aqueous solution are presented for educators interested in explaining or using these methods for their students.
Resumo:
Complete basis set and Gaussian-n methods were combined with Barone and Cossi's implementation of the polarizable conductor model (CPCM) continuum solvation methods to calculate pKa values for six carboxylic acids. Four different thermodynamic cycles were considered in this work. An experimental value of −264.61 kcal/mol for the free energy of solvation of H+, ΔGs(H+), was combined with a value for Ggas(H+) of −6.28 kcal/mol, to calculate pKa values with cycle 1. The complete basis set gas-phase methods used to calculate gas-phase free energies are very accurate, with mean unsigned errors of 0.3 kcal/mol and standard deviations of 0.4 kcal/mol. The CPCM solvation calculations used to calculate condensed-phase free energies are slightly less accurate than the gas-phase models, and the best method has a mean unsigned error and standard deviation of 0.4 and 0.5 kcal/mol, respectively. Thermodynamic cycles that include an explicit water in the cycle are not accurate when the free energy of solvation of a water molecule is used, but appear to become accurate when the experimental free energy of vaporization of water is used. This apparent improvement is an artifact of the standard state used in the calculation. Geometry relaxation in solution does not improve the results when using these later cycles. The use of cycle 1 and the complete basis set models combined with the CPCM solvation methods yielded pKa values accurate to less than half a pKa unit. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001
Resumo:
Complete Basis Set and Gaussian-n methods were combined with CPCM continuum solvation methods to calculate pKa values for six carboxylic acids. An experimental value of −264.61 kcal/mol for the free energy of solvation of H+, ΔGs(H+), was combined with a value for Ggas(H+) of −6.28 kcal/mol to calculate pKa values with Cycle 1. The Complete Basis Set gas-phase methods used to calculate gas-phase free energies are very accurate, with mean unsigned errors of 0.3 kcal/mol and standard deviations of 0.4 kcal/mol. The CPCM solvation calculations used to calculate condensed-phase free energies are slightly less accurate than the gas-phase models, and the best method has a mean unsigned error and standard deviation of 0.4 and 0.5 kcal/mol, respectively. The use of Cycle 1 and the Complete Basis Set models combined with the CPCM solvation methods yielded pKa values accurate to less than half a pKa unit.
Resumo:
The complete basis set methods CBS-4, CBS-QB3, and CBS-APNO, and the Gaussian methods G2 and G3 were used to calculate the gas phase energy differences between six different carboxylic acids and their respective anions. Two different continuum methods, SM5.42R and CPCM, were used to calculate the free energy differences of solvation for the acids and their anions. Relative pKa values were calculated for each acid using one of the acids as a reference point. The CBS-QB3 and CBS-APNO gas phase calculations, combined with the CPCM/HF/6-31+G(d)//HF/6-31G(d) or CPCM/HF/6-31+G(d)//HF/6-31+G(d) continuum solvation calculations on the lowest energy gas phase conformer, and with the conformationally averaged values, give results accurate to ½ pKa unit. © 2001 American Institute of Physics.
Resumo:
The AM1 and PM3 molecular orbital methods have been utilized to investigate the reactions of CH20H with NO and NO2 PM3 and AM1 calculated heats of formation differ from experimental values by 8.6 and 18.8 kcal mol-', respectively. The dominant reaction of CH20H with NO is predicted to produce the adduct HOCH2N0, supporting the hypothesis of Pagsberg, Munk, Anastasi, and Simpson. Calculated activation energies for the NO2 system predict the formation of the adducts HOCH2N02 and HOCH20N0. In addition, the PM3 calculations predict that the abstraction reaction producing CH20 and HN02 is more likely than one producing CH20 and HONO from reactions of CH20H with NO2.
Resumo:
Compliant mechanisms with evenly distributed stresses have better load-bearing ability and larger range of motion than mechanisms with compliance and stresses lumped at flexural hinges. In this paper, we present a metric to quantify how uniformly the strain energy of deformation and thus the stresses are distributed throughout the mechanism topology. The resulting metric is used to optimize cross-sections of conceptual compliant topologies leading to designs with maximal stress distribution. This optimization framework is demonstrated for both single-port mechanisms and single-input single-output mechanisms. It is observed that the optimized designs have lower stresses than their nonoptimized counterparts, which implies an ability for single-port mechanisms to store larger strain energy, and single-input single-output mechanisms to perform larger output work before failure.
Resumo:
This thesis explores system performance for reconfigurable distributed systems and provides an analytical model for determining throughput of theoretical systems based on the OpenSPARC FPGA Board and the SIRC Communication Framework. This model was developed by studying a small set of variables that together determine a system¿s throughput. The importance of this model is in assisting system designers to make decisions as to whether or not to commit to designing a reconfigurable distributed system based on the estimated performance and hardware costs. Because custom hardware design and distributed system design are both time consuming and costly, it is important for designers to make decisions regarding system feasibility early in the development cycle. Based on experimental data the model presented in this paper shows a close fit with less than 10% experimental error on average. The model is limited to a certain range of problems, but it can still be used given those limitations and also provides a foundation for further development of modeling reconfigurable distributed systems.
Resumo:
This thesis presents two frameworks- a software framework and a hardware core manager framework- which, together, can be used to develop a processing platform using a distributed system of field-programmable gate array (FPGA) boards. The software framework providesusers with the ability to easily develop applications that exploit the processing power of FPGAs while the hardware core manager framework gives users the ability to configure and interact with multiple FPGA boards and/or hardware cores. This thesis describes the design and development of these frameworks and analyzes the performance of a system that was constructed using the frameworks. The performance analysis included measuring the effect of incorporating additional hardware components into the system and comparing the system to a software-only implementation. This work draws conclusions based on the provided results of the performance analysis and offers suggestions for future work.