Theoretical studies of o-, m-, and p-benzyne negative ions

Journal of the American Chemical Society

Volumn 118, Issue 47, 1996, Pages 11872-11883

  Nash, John J ^a   Squires, Robert R ^a  

^a PURDUE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BENZENE DERIVATIVE;

ARTICLE; CALCULATION; IONIZATION; THEORY; THERMODYNAMICS;

EID: 0029949644     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9606642     Document Type: Article

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95. The numerically-evaluated frequencies obtained from the MCSCF-(n,m)/3-21G calculations were scaled by a factor of 0.8894, as determined by comparing the experimental zero point vibrational energy for benzene (61.2 kcal/mol) with the value computed from the MCSCF(6,6)/3-21G-derived frequencies (68.8 kcal/mol). The analytically-evaluated frequencies obtained from B3LYP/cc-pVDZ calculations were scaled by a factor of 0.9715, which is similar to the factor recommended by Radom for B3LYP/ 6-31G * derived frequencies (Radom, L. personal communication of unpublished results).
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99. 2> is 0.78). The MPn energies for the delocalized electronic states of 2a and 3a are generally lower than those of the localized electronic states, but the differences change in an erratic manner with increasing level of theory. The perturbatively-estimated triple substitutions in the QCISD(T) and CCSD(T) calculations reduce the energies of the delocalized electronic states of 2a and 3a by 2.4-3.9 kcal/mol, but increase the energies of the corresponding localized electronic states by 0.2-0.7 kcal/mol.
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101. For a discussion of the notion of molecular "shape" in the context of the Born-Oppenheimer approximation, see: Wooley, R. G. J. Am. Chem. Soc. 1978, 100, 1073. For a recent example of the experimental description of a molecule without a definite "shape", see: Lindner, R.; Müller-Dethlefs, K.; Wedum, E.; Haber, K.; Grant, E. Science 1996, 271, 1698.
102. Frequencies and force constants for any nontotally symmetric vibrational motions obtained from MCSCF calculations that employ numerically- rather than analytically-evaluated energy gradients are invariably too high since any symmetry-breaking nuclear displacement used to evaluate the molecular force field by finite energy differences will eliminate the symmetry-constrained configuration mixings within the active space.
103. Equation 2 may not actually provide proper cancellation of electron correlation errors and basis set deficiencies since it is not isogyric, i.e., the total electron spin is not the same for the products and reactants.
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