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2-. While the phosphoryl and sulfuryl groups are more correctly referred to as phosphonato and sulfonato, respectively, we have retained the common usage because it is more widespread in the literature.
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Weinhold, F. NBO 5.0 Program Manual; Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin: Madison, WI, 2001.
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NBO 5.0 Program Manual
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Weinhold, F.1
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During the preparation of this manuscript it was drawn to the authors' attention that caution should be exercised with basis set augmentation using diffuse functions in deletion analysis because of potential effects on the valence space of remote atoms (see Goodman, L.; Sauers, R. R. J. Comput. Chem. 2007, 28, 269-275). Preliminary tests using several different of the example molecules showed slightly lower occupation of d-orbitals upon removal of diffuse functions from basis sets employed in this study. Despite this, the calculated E(2) values appear relatively independent of whether diffuse functions are employed.
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During the preparation of this manuscript it was drawn to the authors' attention that caution should be exercised with basis set augmentation using diffuse functions in deletion analysis because of potential effects on the valence space of remote atoms (see Goodman, L.; Sauers, R. R. J. Comput. Chem. 2007, 28, 269-275). Preliminary tests using several different of the example molecules showed slightly lower occupation of d-orbitals upon removal of diffuse functions from basis sets employed in this study. Despite this, the calculated E(2) values appear relatively independent of whether diffuse functions are employed.
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93
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35648941923
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Deletion analysis involves deletion of the off-diagonal element describing the interaction between the relevant orbitals, followed by a single-pass (SCF) energy re-evaluation. The difference between the original and re-evaluated energies, Edel, provides an estimate of the stabilization energy afforded to the structure by the relevant orbital interaction. There is general agreement between E(2) and E del values when single orbital interactions are being evaluated. However, when the effects of multiple derealization interactions are under simultaneous investigation, as they are here, E(2) and E del values may not display adequate agreement. Because of higher-order coupling effects, summation of E(2) values for each individual orbital interaction may not necessarily correspond to an Edel value calculated by simultaneous deletion of several interaction elements. Consequently, for the sake of consis
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del value calculated by simultaneous deletion of several interaction elements. Consequently, for the sake of consistency only E(2) values are presented here.
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Cheng, H.1
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