Science in Action – or Not

For my first post in 2019, I wish everyone a happy and prosperous New Year. 2018 was a slightly different year than most for me, in that I finally completed and published my chemical bond theory as an ebook; that is something I had been putting off for a long time, largely because I had no clear idea what to do with the theory. There is something of a story behind this, so why not tell at least part of it in my first blog post for the year? The background to this illustrates why I think science has gone slightly off the rails over the last fifty years.

The usual way to get a scientific thought over is to write a scientific paper and publish it in a scientific journal. These tend to be fairly concise, and primarily present a set of data or make one point. One interesting point about science is that if it is not in accord with what people expect, the odds on are it will be ignored, or the journals will not even accept it. You have to add to what people believe to be accepted. As the great physicist Enrico Fermi once said, “Never underestimate the joy people derive from hearing something they already know.” Or at least think they know. The corollary is that you should never underestimate the urge people have to ignore anything that seems to contradict what they think they know.

My problem was I believed the general approach to chemical bond theory was wrong in the sense it was not useful. The basic equations could not be solved, and progress could only be made through computer modelling, together with as John Pople stated in his Nobel lecture, validation, which involved “the optimization of four parameters from 299 experimentally derived energies”. These validated parameters only worked for a very narrow range of molecules; if they were too different the validation process had to be repeated with a different set of reference molecules. My view of this followed another quote from Enrico Fermi: I remember my friend Johnny von Neumann used to say, “with four parameters I can fit an elephant and with five I can make him wiggle his trunk.” (I read that with the more modern density functional theory, there could be up to fifty adjustable parameters. If after using that many you cannot get agreement with observation, you should most certainly give up.)

Of course, when I started my career, the problem was just plain insoluble. If you remember the old computer print-out, there were sheets of paper about the size of US letter paper, and these would be folded in a heap. I had a friend doing such computations, and I saw him once with such a pile of computer paper many inches thick. This was the code, and he was frantic. He kept making alterations, but nothing worked – he always got one of two answers: zero and infinity. As I remarked, at least the truth was somewhere in between.

The first problem I attacked was the energy of electrons in the free atoms. In standard theory, the Schrödinger equation, when you assume that an electron in a neutral atom sees a charge of one, the binding energy is far too weak. This is “corrected”througha “screening constant”, and each situation had its own “constant”. That means that each value was obtained by multiplying what you expect by something to give the right answer. Physically, this is explained by the electron penetrating the inner electron shells and experiencing greater electric field.

What I came up with is too complicated to go into here, but basically the concept was that since the Schrödinger equation (the basis of quantum mechanics) is a wave equation, assume there was a wave. That is at odds with standard quantum mechanics, but there were two men, Louis de Broglie and David Bohm, who had argued there was a wave that they called the pilot wave. (In a recent poll of physicists regarding which interpretation was most likely to be correct, the pilot wave got zero votes.) I adopted the concept (well before that poll) but I had two additional features, so I called mine the guidance wave.

For me, the atomic orbital was a linear sum of component waves, one of which was the usual hydrogen-like wave, plus a wave with zero nodes, and two additional waves to account for the Uncertainty Principle. It worked to a first order using only quantum numbers. I published it, and the scientific community ignored it.

When I used it for chemical bond calculations, the results are accurate generally to within a few kJ/mol, which is a fraction of 1% frequently. Boron, sodium and bismuth give worse results.  A second order term is necessary for atomic orbital energies, but it cancels in the chemical bond calculations. Its magnitude increases as the distance from a full shell increases, and it oscillates in sign depending on whether the principal quantum number is odd or even, which results when going down a group of elements, that the lines joining them zig zag.

Does it matter? Well, in my opinion, yes. The reason is that first it gives the main characteristics of the wave function in terms only of quantum numbers, free f arbitrary parameters. More importantly, the main term differs depending on whether the electron is paired or not, and since chemical bonding requiresthe pairing of unpaired electrons, the function changes on forming bonds. That means there is a quantum effect that is overlooked in the standard calculations. But you say, surely they would notice that? Recall what I said about assignable parameters? With four of them, von Neumann could use the data to calculate an elephant! Think of what you could do with fifty!

As a postscript, I recently saw a claim on a web discussion that some of the unusual properties of gold, such as its colour, arise through a relativistic effect. I entered the discussion and said that if my paper was correct, gold is reasonably well-behaved, and its energy levels were quite adequately calculated without needing relativity, as might be expected from the energies involved. This drew almost derision – the paper was dated, an authority has spoken since then. A simple extrapolation from copper to silver to gold shows gold is anomalous – I should go read a tutorial. I offered the fact that all energy levels require enhanced screening constants, therefore Maxwell’s equations are not followed. These are the basic laws of electromagnetism. Derision again – someone must have worked that out. If so, what is the answer? As for the colour, copper is also coloured. As for the extrapolation, you should not simply keep drawing a zig to work out where the zag ends. The interesting point here was that this person was embedded in “standard theory”. Of course standard theory might be right, but whether it is depends on whether it explains nature properly, and not on who the authority spouting it is.

Finally, a quote to end this post, again from Enrico Fermi. When asked what characteristics Nobel prize winners had in common: “I cannot think of a single one, not even intelligence.”