Election hangover

Recently, I finished reading the last of “Dictator”, the third of Robert Harris’ trilogy nominally about the life of Marcus Tullius Cicero, but just as much about the collapse of the decaying Res Publica. The aim of Roman politicians was to gain power, or imperium. Few actually wanted to achieve anything, other than to put one over their “enemies” (any other Roman who was not helping them gain their power) or to gain the right to govern a province and get rich from the tithes they would impose. There were exceptions. Cato, and to a lesser extent, Cicero, wanted to maintain the “principles of the republic”, even if these were somewhat ill-defined and were bendable for convenience, while Gaius Julius Caesar genuinely wanted reforms, and was prepared to stamp down on the corrupt practices that he, too, had once engaged in.

In some ways, not a lot changes, although everything now is a lot milder. The vitriol slung between Trump and Clinton would be nothing for the times of the Res Publica. Trump said he would have Clinton investigated; Clodius was quite happy to organize a gang to beat a senator senseless. Even Pompey seemed to be almost afraid much of the time, but of course he obeyed the rules and disbanded his legions before returning to Rome. Caesar was not afraid, but then Caesar did not disband his legions, and he got assassinated.

I am always amused at the straw-clutching assertions made by the losing side. Thus we hear that Clinton won the popular vote. She did but that is irrelevant. About half the eligible population did not vote, and there are at least two possible reasons why not. One is, lack of interest. Another is that for many there is the feeling that if you are in a state that has no chance of changing, and you are in the minority, there is no chance your vote will matter, so why bother?.

Another thing that amuses me is the hand-wringing that went on after Trump won. Horrors! The sky was falling! If they were that concerned, why were they not out campaigning for Clinton? My personal view is that there were so many wild statements flung around during campaigning that we could conclude that such statements are necessary to win the election. If so, there could be a serious withdrawal from most of such statements by the winner.

So, is the sky falling? Is Trump going to be a total disaster, as some of the more noisy ones seem to assert? He won by making the most outrageous statements, but arguably that was what he had to do to win with the current voters. If that is true, then guess were the fault lies. But equally, if he is a man prepared to do whatever is required to achieve a goal, then he may very well retract from many of these positions when the goal is to be an effective president. I suppose we have to wait and see how much power Trump will actually have, but the American constitution is specifically designed to limit the power of any president. The president has to do deals with Congress, and even if Congress is majority Republican in both houses, during the election campaign it was clear that not all Republicans are going to back Trump no matter what. Further, Trump seems to be showing signs of dropping his most outrageous assertions.

I think it is far too early to guess what the Trump presidency will be like. My guess is the fight against global warming has not been done favours, although the US has signed the Paris agreement, and I doubt that will be revoked. Trump’s tax plan is similar to what Paul Ryan wants, so that may well get through. International trade may well suffer, and the US could hurt a country like New Zealand. However, whatever happens, the sky will not fall.

That raises the question, what would it take to bring America to its knees? Strictly speaking, it should be impossible, but there is one way: the bulk of the population cooperates in bringing it down. After all, that was why Rome fell. The average Roman decided that the Roman governance was worse than whatever the uncivilized masses could do, at least once the initial rape and pillage was over. So could anything like that happen now, in America? Of course not. However, if you want to have nightmares over something like that, on Dec 2 my ebook ‘Bot War is available, and if nothing else, it might show you how impossible it is. In this story, the general problem is not the terrorists and their robotic war machines, but rather the general population have no faith in their government. Is that lack of faith justified?

Some After-effects of the Earthquake

One of the interesting things about sea life is that the niches are so crowded that sometimes life clings to one very specialist zone. One of my favourite examples was a seaweed that grew on the southwest face of rocks in a harbour in a band of about ten centimeters depth, and then only in a spot that was about twenty meters long! Yes, that was somewhat exceptional, but the principle applies broadly, if not so strictly. Kaikoura is a great place for finding crayfish (rock lobster), and is reflected by the name, and the coast was a great place for other diverse marine life, including seaweed. During the recent quake, the land rose two meters. The places where I described certain seaweeds as originating from in some of my scientific papers are now high and dry, so the descriptions are no longer helpful. But this land rising will also be a serious disruption to marine life in the near intertidal zone because when the life form wants to be a specific distance below sea-level at low king tide, a two meter lift completely alters much of the environment.

This gives an interesting view from the environmentalists: they decree that none of the recently exposed wild-life shall be harvested, and instead be left to die. I am far from convinced this makes sense. Thus paua (a version of abalone) are hemophiliac, and if cut they die. They cannot return to the sea, and they cannot be shifted. What is the point in leaving them rot? I have heard the explanation, the nutrients will go back to the sea, but that is nonsense from my point of view. Such nutrients will only benefit plant life that can absorb it more or less immediately, and the ocean currents take the rest away. Some of the greenies seem incapable of putting numbers to their thoughts. I once saw one criticism of an attempt at aquaculture state that a particular one-acre pool was going to pollute the Pacific Ocean by deoxygenating it. Leaving aside the wave action during storms, and that the aquaculture was for seaweed, the Pacific is so huge such a statement merely displays a total lack of ability at elementary mathematics.

Back to more standard difficulties. Apart from small segments, the land to the north of Kaikoura is a very narrow coastal strip leading to almost vertical hills that are several hundred meters high. To the south there is a little flat land, then the road has to cross some very torn terrain. The earthquake dropped enormous amounts of rock onto the roads, and it will take months to clear reasonable access and stabilize the hills. The town has too little land for a significant airport, and while it has a port for small vessels, large ones cannot be accommodated.

So our TV programs showed tourists being evacuated on a navy transport ship. These are designed to have smaller landing craft that can more or less go anywhere. The tourists were taken out and had to climb a rope ladder to get into a hatch, where they would settle in a fairly mammoth area. The comfort levels would be low, because the military aims to get things done, but not with excessive comfort, but they aim to be able to do things as near to under any circumstances as possible.

Then in another news clip my attention was drawn to a ship just offshore. That did not look like any of ours, and we saw sailors in uniforms that were not like ours, and that was because it wasn’t and they weren’t. This particular ship was from the US navy, that happened to be in the region, and it dropped other activities to offer what help it could. Apparently there were also ships from the Australian and Canadian navies helping. Thank you, US, Canadian and Australian navies. In a disaster like this, one of the great assets of the military is that they get things done, and they have expertise and skills that really help when survival becomes an issue. Meanwhile our army has managed to open some sort of goat track route to get survival equipment in as well. So far, only in their near “go anywhere” trucks.

Meanwhile, in Wellington, it appears a number of buildings are going to have to be demolished. One of the interesting statements about the building code is, it is not designed to ensure a building will survive a major quake and be able to be used thereafter; it is designed so that the building will have enough structural integrity that nobody is going to get killed during the quake. My guess is property investors who have focused on apartments in the Wellington CBD are going to be a bit nervous for a while.

All of which makes my problems look a bit on the pathetic side. As far as I can tell (and with my recent hip replacement I am not yet sufficiently mobile to check a lot) my house has survived more or less intact, my children’s properties are essentially undamaged, and nobody nearby has sustained serious damage. All in all, things have worked out well for us.

So, back to the more mundane. Somehow I have to work out how to promote my latest ebook, ‘Bot War which will be published on December 2. Interestingly, I see some think that under President Trump, the US is headed towards disaster. I don’t think so, but my novel does give an alternative reason why some of what Trump says should be avoided.


Since my last post, things have been happening and there has been material for several posts. I have been in hospital getting a hip replacement, but that is of little importance, other than to me. The United States elected a new President, after what I thought was one of the most bizarre campaigns, and then there was . . . But more of that below.

The surgery and the follow-up care were carried out with professionalism, skill and commitment, and I can assure anyone wondering that New Zealand does have good skilled medical care. One can argue about the politicians’ involvement with health care (and many of us Kiwis do), but I could not have asked for more. While recovering, the election results were coming in, and I had nurses pausing and discussing. Many Americans probably do not appreciate the importance many ordinary people in other countries attribute to their political scene. Of course there is no personal involvement, so we could make our comments in a detached sort of way. I am sure all who are following my blog, or other writings, will have seen enough comments on the actual result, so I shall leave it at that, other than to add that only too many of such comments show some ugly aspects of the writer that probably should not have been shown.

Then it was time to come home. My daughter thought I was being silly coming home because I have some fairly steep steps to climb, but no problem. The hospital had the rule, if you cannot climb up and down steps, you cannot come home, and I had practised. A lot of people commented on how well I was doing, bearing in mind . . . I put that down to three things. First, for weeks before going in I had been doing exercises to strengthen hip muscles. You cannot do anything about what is to be cut, but with bad hips, the muscles around them tend to atrophy through lack of use. You can do something about that. The second, I was determined to do what had to be done, and I think attitude helps. Finally, I had some long-term goals. Simple goals, like being able to walk down the beach in our up-coming summer. Be that as it may, I mention it just in case anybody else is to face such surgery. One can imagine all sorts of things, but it helps if you can focus on the desirable.

So, the day I came home we had, in a 24 hr period, the total average rainfall for November, and here was me hobbling up towards the house. Any moss on concrete, when wet, tends to get slippery, and you need slipperiness under crutches like you need the plague. So, the end of the bad luck?

Nope. I came home on a Saturday, and had a quiet Sunday, but then shortly after midnight, the house started shaking: a 7.8 earthquake. (Equivalent, I have been told, to 5.35 Mt of tnt.) This was centred at Waiau, which is about 40 % of the way between Christchurch and Wellington. This has apparently got international attention, especially “cow island” – three cows stranded on a pillar where the rest of the land had subsided. In one sense it was good this happened at Sunday/Monday midnight because many of the high-rise buildings in the Wellington commercial district lost sheets of glass, and there would have been serious casualties had there been people wandering about down below. Meanwhile, the electricity to the house went out. For me, there was worse to come – just as I was getting back to sleep, the sirens for a tsunami warning started up. No real likelihood of a tsunami where I live, because I am about 70 meters up a hill. But these sirens went on and on.

Then on Tuesday I had to go back and get dressings changed. No problems, except there was a serious storm going on, a number of roads were closed, and I had to hobble both down and up my path to my house. Of course my inconvenience is nothing compared to others’. Apparently, the whole town of Kaikoura has to be evacuated by sea because all land routes to and from it are blocked by huge rock slips. These road closures are all over the country. Earthquake/storms have closed at least 7 roads in the Lower Hutt area where I live, and a good number of houses have had to be evacuated. Then, of course, the aftershocks; 2000 of them. These have ranged as far north as Taupo, (half-way up the north Island) and a number directly under Wellington. A number of high-rise buildings there are under suspicion.

Yes, this has been a period where things have been happening. I just wish they would slow down, or happen somewhere else. I know that is hardly fair to someone else, but I have felt that a quiet spell for recovery would be good.

Why is the Moon so dry?

The Planetary Society puts out a magazine called The Planetary Report, and in the September issue, they pose an issue: why is there more water ice on Mercury than the Moon? This is an interesting question because it goes to the heart of data analysis and how to form theories. First we check our data, and while there is a degree of uncertainty, from neutron scattering as measured from orbiting satellites, Mercury has about 350 times the water than the Moon, not counting whatever is in the deep interior. Further, some of that on the Moon will not be water in the sense we think of water. The neutron scattering picks out hydrogen, and that can also come from materials such as hydroxyapatite, which is present in some lunar rocks. The ice sits in cold traps; parts of the body where the temperature is always below -175 oC. For the Moon, there are (according to the article) about 26,000 km2 cold enough, while Mercury has only 7,000 km2. So, why is the Moon so dry?

Before going any further, it might help some understand what follows if they understand what isotopes are, and what effects they have. The nature of an element is defined by the number of electrons, which also equals the number of protons. For any given number of protons, there may be a variation in the number of neutrons. Thus all chlorine atoms (found in common salt) have 17 protons, and either 18 or 20 neutrons. The two different types of atoms are called isotopes. Of particular interest, hydrogen has two such isotopes: ordinary hydrogen and deuterium with 0 and 1 neutron respectively. This has two effects. The first is the heavier one usually boils or sublimes at a slightly higher temperature and in a gravitational field, is more likely to be at the top, hence ice that spends a lot of time in space tends to be richer in deuterium. The second effect is the chemical bond is stronger for the heavier isotope.

So where do volatiles (water and gases) on the rocky planets come from? I raised some of the issues on where it did not come from earlier: https://wordpress.com/post/ianmillerblog.wordpress.com/564 To summarize, the first option is the accretion disk. That is where Jupiter’s came from. If the body is big enough before the gases are removed, they will remain as an atmosphere. We can reject that. The planets will have had such atmospheres, but soon after formation of the star, it starts spitting out extreme UV/Xray radiation, and intense solar winds, and these strip the volatiles. The evidence that this removed most of the atmosphere from Earth is that some very heavy inert gases, such as krypton and xenon, have heavy isotope enhancements suggesting they have been fractionally distilled, and some of the heavier isotopes were enhanced. These gases are extremely rare, but they also cannot be accreted by any mechanism other than gravity and adsorption, and unless they were so stripped, there would be huge amounts of neon here because physical mechanisms of accretion apply equally to all the so-called rare gases, and neon is very abundant in the accretion disk. However the krypton was accreted, very large amounts of neon would also be accreted. Neon is rare, so most gases that arrived with the krypton would have been similarly removed. As would be water. So after a few hundred million years, the rocky planets were essentially rocks, with only very thin atmospheres. That, of course, is assuming our star behaved the same way as other similar stars, and that the effects of the high energy radiation are correctly assessed.

So, where did our atmosphere and oceans come from? There are only two possibilities: from above and from below. Above means comets and asteroid-type bodies colliding with Earth. Below means the elements were accreted with the solids, and emitted through volcanoes. Which one? This is where the Mercury/Moon data becomes significant. However, as often is the case, there is a catch. Mathematical modeling suggests that the Moon might have changed its obliquity, and once upon a time it was almost lying on its side. If so, and if this occurred for long enough, there would have been no permanently cold points, and the Moon would have lost its ice. It did not, but the questions then are, did this actually happen, did that period last long enough, or did the water arrive on the surface after this tilting?

Back to Earth’s atmosphere. The idea that Earth was struck by comets has been just about falsified. The problem lies in the fact that the comets have enriched deuterium, and there is too much for Earth’s water to have come from there, other than in minor amounts. A similar argument holds for chondrites. It is not the water that is the problem, but rather the solid rock. The isotope ratios of the chondrite rocks do not match Terran rocks. The same applies for the Moon, because the isotope ratios of the surface of the moon are essentially the same as on Earth, and the Moon has not has resurfacing. That essentially requires the water on Earth to have come from below, volcanically. I gave an account of that at https://wordpress.com/post/ianmillerblog.wordpress.com/576

And now we see why the extreme dryness of the Moon is so important: it shows that very little water did land on the Moon from comets and chondrites. Yes, that was shown from isotopes, but it is very desirable that all information is consistent. When you have a set of different sorts of information that lead to the same place, we can have more confidence in that place being right.

The reason why the Moon is so dry is now simple if we accept the usual explanation for how it was formed. The Moon formed from silicates blasted out of the Earth when Theia collided with it. Exactly where Theia came from is another issue, but the net result was a huge amount of silicates were thrown into orbit, and these stuck together to form the Moon. We now come to a problem that annoys me. I saw a review where it said these silicates were at a temperature approaching 1100 oC At that temperature, zinc oxide will start top boil off in a vacuum, and the lunar rocks are depleted in zinc. According to the review, published in October, it could not have been hotter because the Moon is not significantly depleted in potassium. However, in the latest edition of Nature (at the time of writing this) an article argued there was a depletion of potassium. Who is right, and how does whoever it is know? Potasium is a particularly bad element to choose because it separates out and gets concentrated in certain rocks, and we do not have that many samples. However, for water it is clear: the silicates were very hot, and the water was largely boiled off.

So, we have a conclusion. I suppose we cannot know for sure that it is absolutely right because we cannot know there is not some other theory that might explain these facts, but at least this explanation is consistent with what we know.

To conclude, some personal stuff. There will be no post from me next week; I am having hip replacement surgery. Hopefully, back again in a fortnight. Second, for those interested in my economic thoughts, my newest novel, ‘Bot War, will be available from December 2, but it is available for preorder soon.

Voting for Aleppo

With the US elections coming up, and enduring chaos in the Middle East, we have to ask, which is the best candidate to sort that out? I am not exactly enthralled by either of them. First, the scenario. As is well known, the US has supported some “moderate” rebels who have the aim of ousting Assad in Syria, and is supporting the retaking of Mosul, apparently with air power. Russia is supporting Assad in Syria. Turkey wants to deal to ISIS in Mosul. This should have a straight-forward ending?

First, look at religion. Assad has support from Shia, including Hezbollah and Iran. The rebels include some moderates, but the important ones are associated with al Qaeda. So here, Russia is supporting Shia; the US is trying to protect Sunni and terrorists. Assad himself operated a secular government, as did Saddam, so an alien observer would presumably conclude that the US is against secular governments, which makes little sense. In Iraq, the US is supporting the Shia government to take out the fanatical ISIS, and will use air power to bomb the terrorists in Mosul. Or at least, that is a somewhat oversimplified account of what might happen. So, what do the candidates say?

Trump seemingly has not clearly defined policy here. That is not necessarily a bad thing. Leaving the place to sort itself out is a legitimate policy, and may be as good as any. The problem, though, is ISIS and al Qaeda. Left to their own devices, they are hardly likely to be beneficial. A second problem is that it appears Trump has not thought about this at all.

Clinton, however, is in my mind just outright dangerous. She has announced she will have a no-fly zone over Aleppo. That raises many questions. First, why? Does she want to nourish al Qaeda, who, as an aside, have killed far more innocent Western citizens than ISIS by a long shot? The nominal reason is to protect innocent civilians, but there are more in Mosul, and the US intends to bomb that, and, of course, there was “shock and awe”, which led to a very large number of dead Iraqis.

However, there is a much worse possible outcome than killing some innocent civilians, which is most certainly bad, but my worry is much worse. What does she do if the Russian air force continues bombing? Does she order the shooting down of Russian warplanes, which happen to be over the territory of, and at the invitation of, a sovereign government. If so, what is the justification? Because we can? That is a rather slippery slope. The US is actually one of the most warlike countries on the planet, and has been at war most of the time since 1890. It has been able to do this because the war is always “elsewhere”, and they cannot do any damage to the US. The result of this is that much of the population is unaffected by such wars. That does not give the US the right to shoot anyone they feel like, though. Russia has two choices: bow down before America, or ignore the threat.

If Russia bows down, then that establishes a precedent. Everybody expects that to happen again, and that encourages (from the Russian eyes) America to do more or less what it likes. It can order Russia out of the Crimea. Now what? Bow down again? Where does it stop?

If the Russians keep bombing, and the US shoots down at least one Russian warplane, now what? Russia can either bow down, or fight back. We don’t know the Russian capability, but we do know they have some ability, so unlike other recent opposition, Russia might shoot down an American plane, or attack an American base nearby. If the American aircraft came off a carrier, what happens if the Russians sink the carrier? The Russians have a carrier somewhere nearby, so the US sinks it. Now what?

Suppose the aircraft came from Turkey. Can Russia accept a border wherein America can come and shoot them down at will with no downside? It would be strange if they did. But if Russia attacks the base, that is an attack on a NATO country, which America could use to activate the NATO alliance. At this point we note that Russia could have done something more constructive earlier. When Clinton announces the no-fly zone, Russia should announce that any attack on Russia as a consequence of Clinton’s announcement from a NATO country will be taken as a declaration of war from that country on Russia. If the country is an aggressor, that should not trigger the NATO commitment. At the very least, some more nervous countries might decide that getting out of NATO is more desirable. Maybe not, but Russia should offer the option.

Now, suppose some missiles are launched from the Baltic states, and assume they are conventionally tipped. Now what? The least we can expect is that Russia sends all its motor rifle divisions westwards. Now what? Contrary to what some people think, my guess is that NATO would offer only moderate resistance, and indeed some of the countries would pull out of NATO on the grounds that it was not their fault that Clinton started all this. It is one thing to defend against an attack on one of their allies, but something else to get their ally out of a mess of its own making. Further, unless Russia makes good progress and has the ability to walk away from this with its head held high, there is little room for later negotiation.

It is hard to see such a war remaining conventional. The US simply does not have a big enough army to conquer Russia, which is a very big place, and it is far from clear that American soldiers want to fight multi-year wars in some of the world’s worst climate. One of the two will sooner or later resort to the nuclear option and a lot of us will be turned to ash.

Maybe there are other futures following such an edict. The Russians may surrender and comply with Clinton. After a brief skirmish, both parties might see sense, but do we want to bank on that? World War I was started almost accidentally. Do we want to start WW III?

The start of my career

Following on from last week’s post, getting my PhD did not go quite the way I had envisaged. The night before the oral exam, my fiancée terminated the engagement. Just before the oral exam I had arranged to get a smallpox injection, and I was not prepared for the rapidity of what came next. At the end of the exam I was sweating, and not because of the questions. I went to my car, and my left arm was the nearest to being paralysed and I needed it to change gears. Then I found out my mother was going into hospital for breast cancer (the good news was it worked, and she lived for quite a lot longer and she did not die of cancer.)

So, when I went to North America for a post-doc, and being lonely, I had time to work on a paper on strained molecules, and to explain exactly what I thought was going on. Because this was my first scientific paper, I got it wrong. No, not the work, but the presentation. Unless you were a big name, there were strict page limits on what a “newbie” could expect to get published. What I aimed for was to present a general method for calculating the properties of strained molecules that were dependent on the strain. In the associated post, for those interested, I shall give a description of the science as I see it, but for those that are not so interested in that, basically what I wanted to write was a means not only of accounting for what we already knew, but to present an approach that would make predictions for molecules that were yet to be measured, or even made.

The first draft was too long. It involved four parts: a general discussion of strain and the philosophy of the approach, the calculating method, a new proposed method for estimating the strain in a molecule, then the results of the calculations in terms of the ring bending strain in molecules and the resultant dipole moments. I had to shorten the paper so what I did was to cut out most of the first part, because it was “obvious”. It was obvious to me, but it appears nobody else could see it. What I should have done was to cut out the method for estimating the strain in molecules, and submit that as a separate paper because it could stand on its own and it had merit outside the paper I was writing. As I recall, the peer reviewers let it through without comment.

I wrote a series of further papers, and these showed that the properties of strained systems adjacent to charge or unsaturation were properly explained simply through standard electromagnetic theory, and no special quantum effects were required. More importantly, the predictions of parts of the electromagnetic explanation were opposite to those of the quantum delocalization explanation. Thus while both theories predicted that adjacent positive charge would be stabilized, only the electromagnetic explanation predicted that negative charge would be destabilized, so there was a clear and discrete difference between the two possible explanations. A limited number of spectral transitions could be used to separate these two theories, and where electrons moved towards the strain in the excited state, I predicted a shift that was in the opposite direction to delocalization. Even more importantly, experimental results showed I had calculated the shift almost exactly. Standard theory could not even get the direction of the shift right, so in principle the delocalization theory was falsified.

So, what happened? Two reviews came out, asserting the delocalization theory was right. End of story. How did that happen? First there was a review restricted to spectra. The review simply dismissed the few examples such as those I had identified that gave opposite effects for the two theories on the grounds these compounds were not very important!! Real science in action??? There was no mention of my paper on the subject, although it was possible that when that author submitted his review the paper may not yet have been in print.

The second “authoritative review” was much worse, because for no good reason, it ignored all my work. Worse than that, much later I tried to write a counter review, carrying out a logic analysis on all the data as of then. What I found was that there were about sixty different types of observations that were not in accord with the delocalization theory as generally presented. Now, some of those might have been explained away, as always there are some “special circumstances” but sixty is an awful lot. That review could not get published. Reason: the journals “did not publish logic analyses”! So, what did this “authoritative review” do about such papers? Simple. It ignored those as well. Basically, it found what it thought agreed with what it wanted (and some was debatable) and it ignored what it did not want. That, to me, is not real science.

The clincher, in the “authoritative review”, was that molecular orbital computations proved the cyclopropyl ring did delocalize! Quantum mechanics is obviously right, so this must be right. The problem here, of course, is that quantum mechanics produces equations that cannot be solved for systems like this, so all sorts of approximations have to be made. They prove nothing; they might predict something, but in this case they accounted for what we knew, but how? As an aside, calculations from exactly the same school of computations (I.e., the same programs were used) proved the stunning additional stability of polywater.

Never heard of polywater? That was a blot on science. Tiny amounts of water were collected by distilling them through microfine quartz capilliaries, and the water had a much higher boiling point, about 30% higher density, and a much higher viscosity. (That sample had dissolved silica.) It was shown to have a different infrared spectrum to that of water (later to be found to be the spectrum of sweat – another lowlight!)

To illustrate why I distrust computational chemistry, much later a new form of delocalization was proposed. The first such paper (Dewar, M. J. S. J. Am. Chem. Soc. 1984, 106, 669-682.) argued that if bond bending is simple harmonic then (U)bend = kq2, with k the carbon-carbon bond bending force constant, q the angle of deformation from the tetrahedral angle, in which case the strain energy of cyclopropane should be about 437 kJ/mol. It is actually about 120, so he calculated, using molecular orbital theory, a proposed s aromaticity to correct this, and came up with almost exact agreement with observation. Shortly after, there was a counter (Cremer, D.; Kraka, E. J. Am. Chem. Soc. 1985, 107, 3800-3810.) This paper argued the force constant used was wrong, and the strain should be 313 kJ/mol. Then, using exactly the same variant of molecular orbital theory, he calculated a s aromaticity of 200 kJ/mol, again claiming exact agreement with observation. It is impossible (at least for me) to work out where the difference was in the two sets of computations. (My equation for calculating the strain had no excess strain, and the function was proportional to sinq. There is a big difference in functionality between sinq and q2.)

So, I am a sore loser? I should just go away and rejoin the mainstream? Well, I am not entirely alone in this. One of the best current mathematicians and theoretical physicists, Roger Penrose, has just written a book called “Fashion, Faith, and Fantasy in the New Physics of the Universe “. For him, the success of quantum mechanics makes physicists insensitive to the theory’s conceptual problems and generates an unjustified degree of faith in its so-called “basic principles”. Interestingly enough, he cites chemistry as an example of quantum mechanics impressive record. One of the problems with computational chemistry is the equations are insoluble. In his Nobel lecture, Pople introduced the process of validation, which involved “the optimization of four parameters from 299 experimentally derived energies”. This sets the parameters to be used on similar molecules, and as far as I am concerned is not much better than empirical relationships. What happens if the nature of the molecules change? It appears they re-validate. When Moran et al. (2006 J. Am Chem Soc. 128: 9342-9343.) used some computational programs then commonly in place and available as packages for the general chemist, they found that when they applied them to molecules that had been satisfactorily computed earlier, they got wrong answers. The change in validation now lost the ability to calculate earlier molecules, and, as an aside, these errors were dramatic, thus benzene was no longer planar.

That is why I am less than impressed with modern science. It is too ridden with fashion. The reason? I believe it is due to the funding mechanism. Nobody wants to go back over accepted material. If it were yours, you have trouble getting funding the next time. If it were someone else’s, that person had better not be a peer reviewer. Better to go with the flow. My trouble was, I could not get myself to do that.

At the time of the cyclopropane issue, there was another young chemist who carried out an experiment that came to a similar conclusion that there was no delocalization. As things settled down, he abandoned the area, got into a “hot” area, and eventually became very prestigious. I asked him about that paper once and why he left it alone. “Oh that,” he said, with the air of someone who wished I would go away. “That was just . . . ” and he gave a shrug of disinterest. Even if you are right, it is better career-wise to forget it and get back into the flow. Unfortunately for me, that was not the science I signed up for so long ago.

Chemical effects from strained molecules

The major evidence supporting the fact that cyclopropane permits electron delocalization was that like ethylene, it stabilizes adjacent positive charge, and it stabilizes the excited states of many molecules when the cyclopropane ring is adjacent to the unsaturation. My argument was that the same conclusion arises from standard electromagnetic theory.

Why is the ring strained (i.e. at a higher energy)? Either the molecule is based on distorted ordinary C – C bonds (the “strain” model) or it involves a totally new form of bonding (required for delocalization). If we assume the strain model, the orbitals around carbon are supposed to be at 109.4 degrees to each other, but the angle between nuclei is 60 degrees. The orbitals try to follow the reduced angle, but as they move inwards, there is increased electron-electron repulsion, and that is the source of the strain energy. That repulsion “lifts” the electron up from the line between the nuclei to form a “banana” shaped bond. Of the three atoms, each with two orbitals, four of those orbitals come closer to a substituent when the bonds are bent, and the two on the atom to which the substituent is attached maintain a more or less similar distance, because the movement is more rotational.

If so, the strained system should be stabilized by adjacent positive charge. Those four orbitals are destabilized by the electron repulsion from other electrons in the ring; the positive charge gives the opposite effect by reducing the repulsion energy. Alternatively, if four orbitals move towards a substituent carrying positive charge, then as they come closer to a point, the negative electric field is stronger at that point, in which case positive charge is stabilized. The problem is to put numbers on such a theory.

My idea was simple. The energy of such an interaction is stored in the electric field, and therefore it is the same for any given change of electric field, irrespective of how the change of field is generated. Suppose you were sitting on the substituent with a means of measuring the electric field, and the electrons were on the other side of a wall. You see an increase in electric field, but what generates it? It could be that the electrons have moved closer, and work is done by their doing so (because the change of field strength requires a change of energy) OR you could have left them in the same place but added charge, and now the work corresponding to the strain energy would be done by adding the charge. There is, of course, no added charge, BUT if you pretend there is, it makes the calculation that relates the strain energy to the effects on adjacent substituents a lot simpler. The concept is a bit like using centrifugal force in an orbital calculation. Strictly speaking, there is no such force – if you use it, it is called a pseudoforce – but it makes the calculations a lot easier. The same here, because if one represented the change of electric field as due to a pseudocharge, there is an analytic solution to the integration. One constant still has to be fixed, but fix it for one molecule and it applies to all the others. So an alternative reason why adjacent positive charge is stabilized was obtained, and my calculation was very close to the experimental value that was obtained. So far, so good.

The UV spectra could also be easily explained. From Maxwell’s electromagnetic theory, to absorb a photon and form an excited state, there has to be a change of dipole moment, so as long as the positive end of the dipole can be closer to the cyclopropane ring than the negative end, the excited state is stabilized. More importantly, when this effect was applied to various systems, the changes due to different strained rings were proportional to my calculated changes in electric field at substituents. Very good news.

If positive charge were stabilized due to delocalization, so should negative charge be stabilized, but if it were due to my proposed change of electric field, then negative charge should be destabilized. This is where wheels fell off, because a big name published asserting negative charge was stabilized (Maerker, A.; Roberts, J. D. J. Am. Chem.Soc. 1966, 88, 1742-1759.) They reported numerous experiments in which they tried to make the required anion, and they all failed. Not exactly a great sign of stabilization. If they used a method that cannot fail, the resultant anion rearranged. That is also not a great sign of stabilization, but equally it does not necessarily show destabilization because stabilization could be there, but it changes to something even more stable.

Their idea of a clinching experiment was to make an anion adjacent to a cyclopropane ring and two benzene rings. The anion could be made provided potassium was a counterion. How that got through peer review I have no idea because that anion would be far less stable than the same anion without the cyclopropane ring. Even one benzene ring adjacent to an anion is well known to stabilize it. The reason why potassium was required was because the large cation could not get near the nominal carbon atom carrying the charge and that ballowed the negative charge to be destabilized away from the cyclopropane.. If lithium were used, it would get closer, and focus the negative charge closer to the cyclopropane ring. This was a case of a big name able to publish just about anything, and everyone believed him because they wanted to.

Which is all very well, but it is one thing to argue an experiment could have been interpreted some other way, but that is hardly conclusive. However, there was an “out”. The very lowest frequency ultraviolet spectral absorptions of carbonyl compounds were found to involve charge moving from the oxygen towards the carbon atom, and the electric moment of the transition was measured for formaldehyde. My theory now could make a prediction: strained systems should move the transition to higher frequency, whereas if delocalization were applicable, it should move to lower frequency. My calculations got the change of frequency for cyclopropane as a substituent correct to within 1 nm, whereas the delocalization argument could not even get the direction of the shift correct. It also explained another oddity: if there were a highly strained system such as bicyclobutyl as a substituent, you did not see this transition. My reason was simple: the signal moved to such a higher frequency that it was buried in another signal. So, I was elated.

When my publications came out, however, there was silence. Nobody seemed to understand, or care, about what I had done. The issue was settled; no need to look further. So much for Popper’s philosophy. And this is one of the reasons I am less than enthused at the way alternative theories to the mainstream are considered. However, there is a reason why this is so. Besides the occasional good theory, there is a lot of quite spurious stuff circulating. It is easy to understand why nobody wants to divert their attention from the work required for them to get more funding. Self-interest triumphs.

Does it matter? It does if you want to devise new catalysts, or understand how enzymes work.