The Ghost of Paley
Posts: 1703
Joined: Oct. 2005
|
Louis:
| Quote | 4. Googling for concepts you clearly don't understand is not helping you Ghost. Like that article you cited (and clearly didn't read) about orbital collapse, you DO know what they are doing don't you? They are explicitly doing something very "unusual" (in terms of the atom's normal state) to the atoms they are dealing with, by sticking them "in" a certain type of "potential doube well". These are highly "unnatural" and excited atomic states that simply don't apply to ground state atoms in molecules etc. Oh and by the way, orbital collapse is yet another hybridisation. It's not the disappearence or curling up of orbitals. (Oh you haven't explained this curling up of antibonding orbitals when the corresponding bonding orbital hangs around yet, just to remind you) It's nice to see you floundering around for concepts you don't understand, but it's becoming tiring Ghost, stop it. Even an extremely intelligent person with google and Mathematica isn't going to overturn centuries of well understood science in a week (or even several months), and boy, you CLEARLY ain't extremely intelligent!
|
I'd like to focus on a sample of Louis's critique for now, because this response so beautifully illustrates the fruits of contemporary culture.
1) The decay of civility:
Once upon a time, people lived in civilised societies, and these societies encouraged certain standards of behavior when debating strangers or casual acquaintances: a) a focus on arguments rather than individuals, (b) trying to understand the other side's position before criticising it, and, underlying the first two rules, c) a sense of humility before truth.
During the sixties, things began to change. A group of French structualists, existentialists, and Freudian Marxists began to rail at the confines of a life and civilisation that they saw as empty, if not actively destructive. No fixed, objectifiable meaning could be attached to anything; therefore, the individual was free to create his own meaning without reference to any cultural tradition. These ideas resonated among the intelligensia, media, and college students, who, with hands uncalloused by hard labor and a bellyful of lazy, untested ideas, actively loathed the societies that provided them with their unearned privileges. And since it's easier to create than destroy, they decided to wreck what they saw around them, without the foggiest concern about what might take its place. Implicit in the destruction of society was the destruction of the individual, for a thinking individual is always a menace to the deliberately unstudied, even (especially?) in those gossamer philosophies that advocate solipsism & sophistry.
And the word was made flesh, and dwelt among societies in the form of musicians and athletes like Bob Dylan and Muhammad Ali. To people like these, blessed with a supple ignorance shrouded in wordplay and storybook rhymes, the phoenix of success could only emerge from the ashes of another individual's immolation. Donovan, rather than being a catchy tunesmith who stole the less enlightened elements of the Dylan fanbase of beatnik housewives and dopester collegiates, was an enemy who must be ground to powder for outselling the Voice of Aquarius. Joe Frazier wasn't a skilled and dangerous boxer who might give Ali trouble; he was an ugly, stupid gorilla that dared to besmirch a legend by depositing The Greatest on his ass. Thus was born the trash talker, America's gift to the world.
And what a gift it has been! So easy to use, because it requires no thought, and importantly, no connection to a world outside the confines of a juvenile mind. Of course, it doesn't provide much in the way of civilisation, but when one starts with much capital, it takes time to fritter it away. This leads us to:
2) An inability to reflect on forbidden ideas
Let's take orbital collapse for example. I've been suggesting that it might be possible for atomic orbitals to curl up. Louis, of course, rejects this idea, and claims that this merely illustrates my insinkable ignorance of chemical bonding. Orbitals don't decay, they can't decay, and anyone who suggests otherwise must be trafficking in bafflegab. He doesn't even need to discuss the issue, for such is beneath any right-thinking individual. One can only respond with insults, appeals to invincible authority, and lectures on undergraduate chemistry. This, of course, is not meant to extend debate, but to stifle it. And it usually succeeds. Alas, sooner or later the trash-talker encounters an opponent who does not scare, and the results can often be comical.
So, to see if my idea has any legs, let's examine a paper that discusses this very issue. If I'm correct, then we should see an orbital's mean radii shrink. If Louis is correct, then the mean radius will remain unchanged. The authors set the stage:
| Quote | | We have selected Ca@C60 for study. Ca is known to be a rather light but highly correlated atom, for which non-relativistic calculations are appropriate, but a many-body approach is required. As will be shown, Ca develops a unique modification of the properties of transitions upon endohedral confinement, which naturally awakens interest in this atom. Finally, the endohedral fullerene has actually been observed experimentally (Moro et al 1993, Wang et al 1993). |
The authors note later on that:
| Quote | To apply the model theory above to atoms endohedrally confined inside C60, it is logical to fit r© and delta from (1) to the geometrical dimensions of an empty C60. From Xu et al (1996) one finds the inner radius around 3.04 and Å about 5.8 au and the thickness apprx 1.9 au. The potential depth, U, is naturally obtained from experimental data on the negative C60 ion (Wang et al 1991, 1993), which determined the electron affinity of 2.65 eV for C60. A straightforward fit to this energy, for an electron placed inside the empty spherical attractive shell defined above, yields 8.22 eV for U.
|
Now, scroll down to Figure 1, which plots the orbital radius to wavefunction amplitude and check the 4d orbital in particular. You'll see a startling result, which our authors later summarise:
| Quote | Indeed, the 4s, 3d and 5d orbitals behave in accordance with conventional wisdom by transferring some electron density to the attractive shell of C60. The 4d orbital, however, demonstrates a more complicated behaviour. There is not only a significant transfer of electron density of this orbital from the outer space into the attractive shell, but also an additional and significant transfer of the 4d electron density further inside the hollow cage of C60 ,r<rC , which results in a significant increase in the amplitude of the 4d orbital in this inner region. Consequently, the mean radius of the 4d orbital is reduced from around 14au in free Ca to about 4.3au<rC =5.8au in @Ca. Hence, in the latter case, the 4d orbital is largely `packed', or compressed into the hollow cage of the confining shell, so that it is now 4d instead of 3d which has the highest amplitude and concentration of electron density near the atomic core. This is actually a novel effect, namely that even an attractive shell can exert (selectively) positive pressure on an atomic orbital, making its size even smaller than the radius of the confinement itself (by `size' we understand the mean radius of the orbital). We refer to this effect as selective orbital compression (SOC) below.
|
Now, before Louis replies that this is a well-understood consequence of yadda yadda yadda, let's quote the next sentence:
| Quote | | While SOC is still not fully understood, we present here a tentative interpretation for its occurrence. |
So this is not, I repeat, not a well understood phenomenon that my feeble brain can't grasp. The authors admit that it's a bit of a mystery in the end:
| Quote | | We have shown here that endohedral confinement can essentially, and what is more important, selectively alter atomic properties. Of particular interest are (a) the discovery of a selective compression effect, illustrated by the behaviour of the 4d orbital of @Ca inside an attractive shell and (b) the `reversed action' of electron correlations in confined @Ca as compared to free Ca. These unexpected features show that endohedrally confined atoms are a new and exciting subject of investigation. Such atoms possess properties and can exhibit behaviour not previously met or studied in free systems, which can also vary from atom to atom. |
Of course, as the authors note, this is also not a behavior observed in free systems, but that's not the point. The point is that orbitals can exhibit strange properties under certain conditions, which include a very real orbital contraction, contra Louis. Which pretty much blows his claim out of the water.
More later.
--------------
Dey can't 'andle my riddim.
|
?
By the way, I'm going to clarify my first installment a little.... 
