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A rough estimate of the role of Coulomb repulsion in the lowering of the second PA compared to the first can be obtained by determination of the average distance of the charge centers in the two bisguanidinium ions from the computed partial charges.13 For [1+2H]2, in which the charge is mostly concentrated on the guanidine-carbon atom with some contributions from the NH2 groups, the distance of the averaged charge centers amounts to r, 8.4 Å (compared to r, 7.53 Åof the two guanidine-carbon atoms, which results in a lowering of the PA by 1.70 eV only by the effect of Coulomb repulsion. In the case of compound [2+2H]2, in which the charge is mostly concentrated on the N-methyl groups, the distance of the averaged charge centers is larger r, 9.3 Åwhile r, 7.51 Å between the two guanidine-carbon atoms is almost identical to [1+2H]2, resulting in a lowered Coulomb repulsion
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-1), but fails quantitatively because through-bond repulsion via polarization as well as resonance effects are entirely neglected in this simplistic electrostatic approach.
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For an elaborate discussion of the concept of ion/neutral complexes, their classification, and the difficulties to locate loosely bound intermediates computationally, see:, Nibbering, N. M. M, Ed, Elsevier, Oxford, U.K
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For an elaborate discussion of the concept of ion/neutral complexes, their classification, and the difficulties to locate loosely bound intermediates computationally, see: Morton, T. H. In The Encyclopedia of Mass Spectrometry; Nibbering, N. M. M., Ed.; Elsevier, Oxford, U.K., 2005; Vol. 4, p 542.
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Taken from: NIST Standard Reference Database Number 69; NIST: Gaithersburg, 2005, see: http://webbook.nist.gov/chemistry/.
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Taken from: NIST Standard Reference Database Number 69; NIST: Gaithersburg, 2005, see: http://webbook.nist.gov/chemistry/.
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See also: a
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See also: (a) Schröder, D.; Harvey, J. N.; Schwarz, H. J. Phys. Chem. A 2000, 104, 11257.
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Unfortunately, the software of the LCQ does not allow the simultaneous mass-selection of two ions, but there are no principal restrictions to such an approach
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Unfortunately, the software of the LCQ does not allow the simultaneous mass-selection of two ions, but there are no principal restrictions to such an approach.
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