Meaningful mutuality

Our objective in re-examining the 1446 pieces of Small Boy data has been to extract the maximum amount of information and the minimum amount of misinformation with the least amount of tampering. Our method has turned out to be a loop which we have traveled innumerable times. The first step of the loop was to choose, for a given laboratory, the best substantiated correlation available and select the outliers. We next traced the outliers through every other meaningful correlation to corroborate their spuriousness. The procedure was repeated for the next best substantiated correlation, and so on, as far as we could carry it. The data from the other laboratories were treated similarly in turn. We have thus examined the data exhaustively for mutual consistency. In many cases we were able to show that a datum violated more than one criterion, and we rejected it on that basis. In other cases, data were so far out of line that there was no question as to their abnormality. In still other situations we found that correlations could be established with the data from one laboratory but not with the data from another. We then rejected the irregular data in toto. 

It would seem obvious that knowledge in the language of chemical communication, written in the alphabet of molecular structures, is in fact a mandatory condition to establish meaningful and mutually beneficial interactions between mankind and the environment. Only with the accumulation of this knowledge will we eventually be able to stop our endless wars with Nature in futile attempts to exterminate harmful species, to communicate with them, and to exert reasonable control over their activity. Clearly this ultimate goal is still a remote prospect, but it will not be realized without the help of synthetic chemists. 

It is possible to observe NOEs for protons that are bonded to sp3, sp2 or sp carbons. The effect is best observed for methine (R3C-H) protons, though it can be demonstrated for methylene (R2CH2) protons also. It is less easy to observe for methyl (CH3) protons, because methyl protons contribute mutually to the dipole-dipole relaxation of each other. A methine proton, being bonded to three carbons that do not assist in dipole-dipole relaxation, shows an NOE more readily. Therefore, in the case of a closely separated proton, Ha, and a methyl group C(Hb)3 in a molecule, irradiation at the methyl proton frequency results in an enhancement of the Ha absorption, whereas irradiation of Ha will not usually result in a meaningful enhancement of the methyl group absorption. However, as indicated later in this section, it is possible to obtain small NOEs for certain methyl groups. 

In Table 6 we list the results for the C2 molecule obtained with the EOM-CCSDT-3 and full T approaehes for several basis sets. We observe that the differences between the approximate and the rigorous scheme are stable indicating that the mutual interrelations between the method do not depend on the basis set quality and size. Due to the cancellation of the errors the approximate scheme gives results eloser to the experimental values, but - of course - this is not meaningful for the general case. 

Reliability and validity are bound together in a complex way. These two terms sometimes overlap and at other times are mutually exclusive. Reliability generally is easier to understand as it is a measure of consistency. The relationship between reliability and validity can be explained like this if scores are not reliable, they are not valid scores need to be stable and consistent first before they can be meaningful. Additionally, the more reliable the scores from an instrument, the more valid the scores may be. However, scores may still not measure the particular construct and may remain invalid. The ideal situation exists when scores are both reliable and valid. 

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