A Comparison of Density‐Functional Theory and Hartree?Fock Modeling of Organolithium Equilibria |
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| Authors: | Andrew Streitwieser Yew Hung Leong |
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| Institution: | Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720‐1460, USA |
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| Abstract: | Experimental values for a number of organolithium equilibria in THF solution expressed as pK values are compared with computational results at several theory levels. Solvation effects are considered only by coordination of lithium with two THF molecules. Best results are obtained with the hybrid density‐functional method mPW1PW91, which gives satisfactory results over a range of almost 40 pK units, but explicit thermal corrections to 25° are required. |
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| Keywords: | Ion pair acidity Isodesmic equation Ab initio calculations Density‐functional theory (DFT) Microsolvation |
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