Natural resonance theory: III. Chemical applications

Journal of Computational Chemistry

Volumn 19, Issue 6, 1998, Pages 628-646

  Glendening, E D ^a,b   Badenhoop, J K ^a,c   Weinhold, F ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

^b INDIANA STATE UNIVERSITY   (United States)

^c WEST VIRGINIA UNIVERSITY   (United States)

Author keywords

Bonding; Chemical; Natural resonance theory; Resonance theory

Indexed keywords

EID: 15044348102     PISSN: 01928651     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1096-987X(19980430)19:6<628::AID-JCC5>3.0.CO;2-T     Document Type: Article

References (66)

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4. L. Pauling and F. W. Wheland, J. Chem. Phys., 1, 362 (1933); H. Eyring, J. Walter, and G. E. Kimball, Quantum Chemistry, Wiley, New York, 1944, pp. 249-254.
5. L. Pauling, The Nature of the Chemical Bond, 3rd ed., Cornell University Press, Ithaca, NY, 1960.
6. For an authoritative description of standard ab initio computational methods and basis set designations referred to herein, see W. J. Hehre, L. Radom, P. v. R. Schleyer, and J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, 1986.
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9. F. Weinhold, NBO 4.0 Program Manual, University of Wisconsin Theoretical Chemistry Institute, Madison, 1994, Sect. B.8; J. K. Badenhoop, Ph.D. Thesis, University of Wisconsin, Madison, 1994.
10. E. D. Glendening, R. Faust, A. Streitwieser, K. P. C. Vollhardt, and F. Weinhold, J. Am. Chem. Soc., 115, 10952 (1993).
11. 2, to the two twisted orientations of orthogonal pi bonds) map onto a single Lewis diagram, as in (3.1a), the diagram is labelled with their combined weight (49.7%). However, multiple equivalent Lewis diagrams are specified by giving the calculated weighting for one member of the set, followed by the multiplicity in parentheses, as for the two equivalent triple-bonded structures (3.1b).
12. 4h symmetry (corresponding to the fact that π → π* NBO delocalizations are rigorously absent in this case; see below).
13. For brevity's sake, in the following, we display only the leading resonance structure contributions, showing all reference structures [bracketed] and, in some cases, the few most important secondary structures. Although the weights of neglected structures are generally significantly smaller than those displayed, their cumulative contribution can be appreciable, as, e.g., in (2.7). Additional details of neglected structures are available from the authors.
14. K.-T. Lu, G. C. Eiden, J. K. Badenhoop, F. Weinhold, and J. C. Weisshaar, in, T. Baer, C. Ng, and I. Powis (eds.), Current Topics in Ion Chemistry and Physics, Vol. IV: Highly Resolved Laser Photoionization and Photoelectron Studies, Wiley, New York, 1994.
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16. CC = 1.52 Å).
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18. 34 = 1.3376).
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21. Note, however, that more quantitative comparisons of two systems should be based on a common number of comparable reference structures. [For example, (3.2) can be compared directly with (3.1), but not with (3.3); the latter involves a smaller set of reference structures.] The NRTSTR keylist can be used to stipulate a comparable set of reference structures (see, e.g., the examples in the penultimate text section) when the default reference structures for two molecules are dissimilar.
22. In the Pauling-Wheland "covalent-ionic resonance" formalism, each structure in (3.5) would therefore correspond to significant contributions from more highly ionic structures, such as (Matrix Presented)
23. A more comprehensive discussion of the important topic of resonance in amides and related groups is reserved for a forthcoming paper.
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25. See, e.g., C. A. Coulson, Valence, Oxford University Press: London, 1961, pp. 128-138; reference 4, Section 3.1; J. Braunstein and W. T. Simpson, J. Chem. Phys. 23, 176 (1955). The notion of a fundamental dichotomy between ionic and covalent "types" (espoused by Langmuir, Sidgwick, and Sugden) was opposed by Lewis, Mulliken, and others; see the general historical discussion in Jensen (reference 25), pp. 74-77.
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28. In Pauling-Wheland theory, the origins of internal rotation barriers were not linked to resonance interactions such as (4.2), but instead were attributed to d- and f-orbital contributions to bonding hybrids (reference 4, pp. 130-134).
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