TY - JOUR
T1 - Observations and descriptions versus explanations-an example
T2 - Does nature, does theory know about steric hindrance?
AU - Schwarz, W. H.Eugen
AU - Schmidbaur, Hubert
PY - 2012/4/10
Y1 - 2012/4/10
N2 - Quantum chemical investigations in the literature sometimes underpin traditional chemical concepts (such as those of different primary and secondary types of chemical bonding or of steric repulsions) but sometimes also seem to undermine them. Conceptual pitfalls in recent discussions in this and other leading journals, when combining empirically and quantum chemically based reasoning, can be avoided when taking four points into account: 1) The construction of theoretical concepts should be guided by both, physical rigor and the aim of recovering the notions that have been found chemically fruitful. 2) Partitioning of a chemical phenomenon into elementary physical steps should not only consider the stationary initial and final states but also include non-stationary intermediate states that exhibit the physically characteristic internal relaxation mechanism. 3) Even if sufficiently accurate, the partitioning into large contributions of opposite sign is less valuable for a qualitative chemical understanding, as long as the trend of one big decisive term or sum of terms cannot be made obvious (for instance on the basis of the variation principle-or by chemical intuition). 4) Causal explanatory notions, even if more vague or fuzzy than some more rigorous and unique descriptive concepts, have to be advanced towards a more fruitful chemical theory.
AB - Quantum chemical investigations in the literature sometimes underpin traditional chemical concepts (such as those of different primary and secondary types of chemical bonding or of steric repulsions) but sometimes also seem to undermine them. Conceptual pitfalls in recent discussions in this and other leading journals, when combining empirically and quantum chemically based reasoning, can be avoided when taking four points into account: 1) The construction of theoretical concepts should be guided by both, physical rigor and the aim of recovering the notions that have been found chemically fruitful. 2) Partitioning of a chemical phenomenon into elementary physical steps should not only consider the stationary initial and final states but also include non-stationary intermediate states that exhibit the physically characteristic internal relaxation mechanism. 3) Even if sufficiently accurate, the partitioning into large contributions of opposite sign is less valuable for a qualitative chemical understanding, as long as the trend of one big decisive term or sum of terms cannot be made obvious (for instance on the basis of the variation principle-or by chemical intuition). 4) Causal explanatory notions, even if more vague or fuzzy than some more rigorous and unique descriptive concepts, have to be advanced towards a more fruitful chemical theory.
KW - chemical bonding
KW - chemical concepts
KW - computational chemistry
KW - nucleophilic substitution
KW - steric hindrance
UR - http://www.scopus.com/inward/record.url?scp=84859320383&partnerID=8YFLogxK
U2 - 10.1002/chem.201102687
DO - 10.1002/chem.201102687
M3 - Review article
AN - SCOPUS:84859320383
SN - 0947-6539
VL - 18
SP - 4470
EP - 4479
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 15
ER -