Chemistry of vibronic coupling. 3. How one might maximize off-diagonal dynamic vibronic coupling constants for intervalence charge-transfer (IVCT) states in an ABȦ system (A, B = alkali metal, H, halogen)?

Journal of Physical Chemistry A

Volumn 104, Issue 43, 2000, Pages 9740-9749

  Grochala, Wojciech ^a   Hoffmann, Roald ^a  

^a Department of Obstetrics Gynecology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHARGE TRANSFER; ELECTRONIC STRUCTURE; HALOGEN COMPOUNDS; INTERMETALLICS; OPTIMIZATION;

INTERHALOGEN SPECIES; INTERVALENCE CHARGE TRANSFER (IVCT); VIBRATIONAL STRUCTURE; VIBRONIC COUPLING CONSTANTS (VCC);

MOLECULAR VIBRATIONS;

EID: 0034322460     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp0017745     Document Type: Article

References (30)

1. cg. For definition of V, see Methods of Calculations.
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3. See excellent reviews: (a) Bersuker, I. B.; Polinger, V. Z. Vibronic Interactions in Molecules and Crystals; Springer-Verlag: Berlin, 1989.
4. (b) Wong, K. Y.; Schatz, P. N. A Dynamic Model for Mixed-Valence Compounds. Progress in Inorganic Chemistry; Lippard, S. J., Ed.; John Wiley and Sons: New York, 1981; Vol. 28, p 369.
5. Bersuker, I. B.; The Jalm-Teller Effect and Vibronic Interactions in Modern Chemistry; Plenum Press: New York, 1984.
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14. In the case of interhalogen species these are also halogen centers.
15. m- subunits (four atoms).
16. If this is not the case, it is necessary to include additional terms corresponding to low-lying excited states; the first-order perturbation treatment used to obtain eq 1 is inadequate.
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18. More precisely, V used in BCS describes coupling via phonons in the solid state and not via normal modes of molecular systems.
19. For more detailed description of different types of coupling constants see ref 3.
20. Grochala, W.; Hoffmann, R. submitted to Chem. Phys. (No. 1).
21. A probing step was 0.025 Å.
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23. (a) Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J. Chem. Phys. 1980, 72, 650.
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25. Dunning, T. H., Jr.; Hay, P. J. In Methods of Electronic Structure, Theory, Vol. 2, Schaefer, H. F.; III, Ed.; Plenum Press: 1977.
26. We have observed that using eq 9 instead of eq 6 (i.e., setting Δ = 0) may lead to very different values of k and V than in an adiabatic picture. Hence, the assumption of diabacity is essentially not valid if one wants to treat all molecules coherently.
27. i}.
28. as (see Figure 3) are not physical. We take these "unreal" structures as models for studying the VCC for IVCT process, regardless of the their thermodynamic instability.
29. It is possible to define f in the same way as for diatomics, because ABA molecules contain atoms of two and not three different types.
30. Grochala, W.; Hoffmann, R. J. Amer. Chem. Soc., submitted.