Comments on "is it time to retire the hybrid atomic orbital?"

Journal of Chemical Education

Volumn 89, Issue 5, 2012, Pages 570-572

  Landis, C R ^a   Weinhold, F ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

Covalent bonding; First year undergraduate general; Lewis structures; Misconceptions discrepant events; MO theory; Physical chemistry; Quantum chemistry; Upper division undergraduate; Valence bond theory; VSEPR theory

Indexed keywords

EID: 84861563192     PISSN: 00219584     EISSN: None     Source Type: Journal    
DOI: 10.1021/ed200491q     Document Type: Article

References (21)

1. Grushow, A. J. Chem. Educ. 2011, 88, 860-862.
2. Hoffmann, R.; Shaik, S.; Hiberty, P. C. Acc. Chem. Res. 2003, 36, 750-756.
3. Weinhold, F.; Landis, C. R. Valency and Bonding: A Natural Bond Orbital Donor-Acceptor Perspective; Cambridge University Press: Cambridge, London, 2005; p 112.
4. Glendening, E. D.; Badenhoop, J. K.; Weinhold, F. J. Comput. Chem. 1998, 19, 628-646.
5. Reed, A. E.; Weinhold, F. J. Chem. Phys. 1985, 83, 1736-1740.
6. Weinhold, F.; Landis, C. R. Valency and Bonding: A Natural Bond Orbital Donor-Acceptor Perspective; Cambridge University Press: Cambridge, London, 2005; p 563ff. http://www.chem.wisc.edu/~nbo5/tut-cmo.htm (accessed Feb 2012). As illustrated in these references, there are actually many advantages in avoiding the superfluous canonical delocalization.
7. Of course, at the more superficial Koopmans-theorem level, the individual orbital energies of NBOs or NLMOs provide different estimates of ionization energies than those of CMOs, but the former (although still crude) are actually superior to CMO-based counterparts in many Koopmans-style rationalizations of PES phenomena (Weinhold, F.; Landis, C. R. Valency and Bonding: A Natural Bond Orbital Donor-Acceptor Perspective; Cambridge University Press: Cambridge, London, 2005; p 119-125).
8. Grushow's two relevant literature citations ( Purser, G. H. J. Chem. Educ. 1999, 76, 1013-1018;
9. Galbraith, J. M. J. Chem. Educ., 2007, 84, 783-787) are misleading in this context.
10. The Purser article is based on numerous factual errors and misrepresentations that are discussed in a subsequent article ( Weinhold, F. J. Chem. Educ. 2005, 82 526-527).
11. The Gailbraith article essentially concurs with our viewpoint (stating that "the 'failures' of VB are really just due to oversimplification") and adopts VB-type computational methods to confirm that antiquated "d-orbital participation" models of main-group hypervalency are incorrect, in essential agreement with previous NBObased and other studies ( Kutzelnigg, W. Angew. Chem., Int. Ed. 1984, 23, 272;
12. Reed, A. E.; Weinhold, F. J. Am. Chem. Soc. 1986, 108, 3586;
13. Magnusson, E. J. Am. Chem. Soc. 1990, 112, 7940;
14. Suidan, L.; Badenhoop, J. K.; Glendening, E. D.; Weinhold, F. J. Chem. Educ. 1995, 72, 583).
15. See, e.g., Nahum, T. L.; Mamlok-Naaman, R; Hofstein, A; Kronik, L. J. Chem. Educ. 2008, 85, 1680. Note that the current overemphasis on delocalized models is partially due to the fact that electronic structure programs commonly present SCF solutions in the CMO form that is most convenient for numerically solving SCF equations, rather than in the unitarily equivalent localized form. However, many such packages now include NBO software [http://www.chem.wisc.edu/ ~nbo5 (accessed Feb 2112)] that can "undo" canonical delocalization and present the solutions in the intuitive, transferable NBO/NLMO form that corresponds directly to localized bonding models.
16. Heilbronner, E. In Daudel, R.; Pullman, B., Eds.; The World of Quantum Chemistry; D. Reidel: Dordrecht, 1974; p 211.
17. Potts, A. W.; Williams, T. A.; Price, W. C. Faraday Discuss. Chem. Soc. 1972, 54, 104-115.
18. Shaik, S. S.; Hiberty, P. C. A Chemist's Guide to Valence Bond Theory; Wiley-Interscience: New York, 2008; pp 104-116.
19. Bent, H. A. Chem. Rev. 1961, 61, 275; ref 3, p. 138ff.
20. Weinhold, F.; Landis, C. R. Valency and Bonding: A Natural Bond Orbital Donor-Acceptor Perspective; Cambridge University Press: Cambridge, London, 2005; p vii.
21. Schreiner, P. R. Angew. Chem., Int. Ed. 2002, 41, 3579-3582.