ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
A systematic procedure based on the sequential Monte Carlo quantum mechanics (S-MC/QM) methodology has been used to obtain hydrogen bond strength and structures in liquids. The system considered is pyridine in water. The structures are generated by NVT Monte Carlo simulation, of one pyridine molecule and 400 water molecules. The hydrogen bonds are obtained using a geometric and energetic procedure. Detailed analysis shows that 62% of the configurations have one hydrogen bond. In the average, pyridine in liquid water makes 1.1 hydrogen bonds. The sampling of the structures for the quantum mechanical calculations is made using the interval of statistical correlation obtained by the autocorrelation function of the energy. A detailed statistical analysis is presented and converged results are obtained. The QM calculations are performed at the ab initio MP2/6-31+G(d) level and the results are compared with the optimized 1:1 cluster. Our results using QM calculations on 155 structures making one hydrogen bond gives an average binding energy of 3.7 kcal/mol, after correcting for basis set superposition error, indicating that in the liquid the binding energy is about 2/3 of the corresponding binding in the optimized cluster. © 2002 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.1485963
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