> The increased nuclear mass causes orbiting electrons to speed up to a significant fraction of the speed of light, where the rules of Einstein’s theory of relativity are important.
> In the relativistic regime, an electron’s spin — the magnetic moment that points either up or down — and the electron’s orbit are no longer independent of each other, a state known as spin-orbit coupling.
Interesting stuff. I've never heard of sigma or pi bonds.
Sigma and Pi bonds are typically covered in AP Chemistry, even if the “why/how” is hand waved pretty heavily. The valence cloud shapes get wild for heavier atoms and bonds between two or more atoms add even more to the mix.
I had incredible difficulties with Chemistry, more than any other subject, because most everything was hand waved away, requiring mostly rote memorization. I could never get an intuitive understanding, partly because my profs seemingly refusing to think about things from a physics perspective. My physics prof was able to help with some of it. It was very odd.
If I would have stuck with it, would things have improved?
Part of the problem is that the difficulty curve becomes, like, superexponential if you try to do the actual math. Fairly elementary atoms require the full theory of quantum mechanics to justify rigorously, and anything more complicated than that requires huge bodies of specialist knowledge on approximation schemes (I assume; I haven't studied them, but given that helium already requires approximations I'm assuming the trend continues..)
Of course, they could still do a much better job useful providing pointers into this knowledge, instead of just handwaving over it and insisting on rote memorization.
But oftentimes theoretical chemistry is not as important as what we get out of experiments because unlike physics, which attempts to derive general laws of nature, chemistry has to deal with the nitty gritty of the diversity of actual miscroscopic interactions of things. Any theory that is not entirely rigorous or even has slight room for an exception will be ignored by necessity, and physics is chock full of such examples. Biology is in a certain sense better (since it deals with larger things) and in a certain sense worse (as it relies on dogma and mysticism, at its essence, to explain the systems of life), and still nobody has gone beyond Aristotle and Kant in giving anything close to a rigorous definition of life as such.
At upper undergrad and grad levels, it probably would have improved a lot. The issue is that a lot of the why requires quantum mechanics to really explain and even that becomes intractable extremely quickly. Like you can probably do the analytic solutions for hydrogen atoms and electrons but once you get to helium or past that, you basically need to use a computer to do numeric calculations and even there, you are very quickly using approximations instead of solving the quantum equations directly.
I don't know, I'm not very chemical, but fwiw: a friend and I were favorably impressed with Linus Pauling's general chemistry textbook. It tries to supply enough of the physics for the chemistry to make sense. We only studied for a few weeks before moving on, though, and it's a big fat book.
I think this lines up with my experience. The way chemistry is often taught its very abstract, borderline magical.
I also had an amazing physics professor who was able to tie literally everything we learned back to real practical and observable events. There is an art to teaching these subjects. This is all undergrad level though, and it wasn’t my major.
Yes and no. It depends which branch of chemistry you world have chosen to go down. Physical Chemistry certainly improves a fair amount of the hand waving, but even there the underlying physics is simplified fairly often (as I understand it — I went straight Physics and dabbled in Chemistry from the other side).
As a chemical engineer, one of the signs of maturity was myself and each of my classmates individually coming to accept and embrace the inevitable “magic coefficient”.
The curious always wanted to know why some magic coefficient was there. Where did it come from? How is it measured / calculated? How to derive the magic coefficient?
Eventually you learn that it’s turtles all the down. You can pick apart the magic coefficient and dive into the nuanced physics that its derived from…but then you still end up with a new magic coefficient.
So eventually, the curious students learn that the mysteries are out there for when you want to go out and explore them. But otherwise, we pick our level of abstraction for the problem we’re currently working on and accept the magic coefficients that apply to that level of abstraction.
The real trick is knowing the conditional boundaries when those magic coefficients no longed apply and you either need different ones or “here be dragons”.
Not in undergraduate chemistry at least. Maybe chem majors had it different. Organic chemistry 1 was basically rote memorization of various reactions and catalysts and their required conditions. Exam questions would be some organic molecule start and some organic molecule end result and you'd have to draw out each and every intermediary step to get to that end result. Organic chemistry 2 was exactly the same just more reactions to memorize. Biochem was a little easier since the exams didn't ask for full pathways but still pretty much pure memorization.
I hated these sorts off classes, where if you had your notes with you, you'd ace the exam and be able to explain everything. Passing or failing depended not on understanding, but simply whether you cram all the specifics and covered edge cases all into your head at once, given the rest of your present courseload preventing you from actually digging in to the best you could. Wrong answers didn't come from not knowing how to solve something, but not remembering exactly how to solve something.
You had a poor organic course. Even orgo 1 should have you thinking about resonance + electron-rich or -deficient areas of molecules and how those lead to reactions.
Of course we talked about those. But if you went off only those you'd miss the edge cases and gotchas the prof laid for you in step 8 of the synthesis. Couldn't get around just doing worksheet after worksheet after worksheet of reactions to try and drive it into your head. Going to office hours to beg for more practice reactions. Everyone scheduled the rest of their major around when they would have to take ochem to make sure the rest of it was as light as possible. Uncurved class averages would be in the 50s.
Pi and sigma bonds fall out of thinking of it from a physical/symmetrical/statistical perspective. There's not too much hand waving in the modeling of atomic and molecular orbitals.
Yes its like cooking or music. You start just by learning whats in the kitchen and on repeating steps. This creates latent or tacit knowledge that helps with the Why questions down the road.
The physics that predicts chemistry is about 100 years old. Almost nothing people study up to high-school is that recent, and that modern physics tends to be really hard.
Yes but ... after a few not so mild assumptions, it takes exponential time to solve it. In this case, you need 6 electrons in 2x5 orbitals for the Carbon and 82 electrons and 2x43 orbitals for Bismuth- (perhaps more, I usually work with lighter atom). So now the free parameter are Combinatoric(96,88)~=3E13 and you must construct a matrix of [3E13 x 3E13] and then find the minimal eigenvalue. So you must make a lot of simplifications and more assumptions to get the result before the universe dies.
And this is for a very cold isolated molecule like in this experiment. If you have many moving molecules surrounded by a lot of water molecules at a usual room temperature, it gets much much much worse.
this was my experience as well. "here's a trend, it's not true in these cases for reasons we won't explain." I only had two semesters and the second was much better than the first.
that's because chemistry is heavily involved in describing the nature of how elements and molecules interact with each other. There has to be some element of understanding that nothing is quite as clear because we use experiments and their conclusions to slowly but surely eliminate some theories while keeping others until disproven.
Granted I took AP Chem 20 years ago, but I don't remember those names (sigma and pi bonds) being covered at all. (I got a 5 on the test, for what it's worth.)
I also took it 20 years ago but I feel like they were (of course I also did undergrad chem 16 years ago so I may be conflating things). It's difficult to explain isomers without explaining why multiple bonds don't rotate.
Wait... wasn't it already understood that relativity influences electron orbits of heavy elements? I clearly remember being taught some of this in physics, in the mid-noughties.
For instance, we know that gold gets its color from relativistic effects.
Seems to be the first time this was confirmed via direct experimental observation of the orbitals:
“This idea that relativity is important in heavy elements has been around since the 1970s,” said Lai-Sheng Wang, a professor of chemistry at Brown and the study’s corresponding author. “But we show direct spectroscopic evidence that what we learned in high school about chemical bonding isn’t true in heavy elements."
The Dirac equation which is the equation for describing the wavelike behavior of electrons. It predicted the existence of antimatter and particle spin.
You start with the Schrödinger equation, add relativity to get the Klein-Gordon equation which is a mess because it's second order in time involving negative probabilities, if you in ways "take the square root" of it you get the Dirac equation.
Relativity has been part of the understanding of electrons since 1928.
Relativity is also responsible for a lot of weird behaviors of heavy elements, such as the color of gold. Or that lead is a good material for batteries.
> The increased nuclear mass causes orbiting electrons to speed up to a significant fraction of the speed of light, where the rules of Einstein’s theory of relativity are important.
> In the relativistic regime, an electron’s spin — the magnetic moment that points either up or down — and the electron’s orbit are no longer independent of each other, a state known as spin-orbit coupling.
Interesting stuff. I've never heard of sigma or pi bonds.
https://www.science.org/doi/10.1126/science.aei1285
Sigma and Pi bonds are typically covered in AP Chemistry, even if the “why/how” is hand waved pretty heavily. The valence cloud shapes get wild for heavier atoms and bonds between two or more atoms add even more to the mix.
I had incredible difficulties with Chemistry, more than any other subject, because most everything was hand waved away, requiring mostly rote memorization. I could never get an intuitive understanding, partly because my profs seemingly refusing to think about things from a physics perspective. My physics prof was able to help with some of it. It was very odd.
If I would have stuck with it, would things have improved?
Part of the problem is that the difficulty curve becomes, like, superexponential if you try to do the actual math. Fairly elementary atoms require the full theory of quantum mechanics to justify rigorously, and anything more complicated than that requires huge bodies of specialist knowledge on approximation schemes (I assume; I haven't studied them, but given that helium already requires approximations I'm assuming the trend continues..)
Of course, they could still do a much better job useful providing pointers into this knowledge, instead of just handwaving over it and insisting on rote memorization.
But oftentimes theoretical chemistry is not as important as what we get out of experiments because unlike physics, which attempts to derive general laws of nature, chemistry has to deal with the nitty gritty of the diversity of actual miscroscopic interactions of things. Any theory that is not entirely rigorous or even has slight room for an exception will be ignored by necessity, and physics is chock full of such examples. Biology is in a certain sense better (since it deals with larger things) and in a certain sense worse (as it relies on dogma and mysticism, at its essence, to explain the systems of life), and still nobody has gone beyond Aristotle and Kant in giving anything close to a rigorous definition of life as such.
At upper undergrad and grad levels, it probably would have improved a lot. The issue is that a lot of the why requires quantum mechanics to really explain and even that becomes intractable extremely quickly. Like you can probably do the analytic solutions for hydrogen atoms and electrons but once you get to helium or past that, you basically need to use a computer to do numeric calculations and even there, you are very quickly using approximations instead of solving the quantum equations directly.
I don't know, I'm not very chemical, but fwiw: a friend and I were favorably impressed with Linus Pauling's general chemistry textbook. It tries to supply enough of the physics for the chemistry to make sense. We only studied for a few weeks before moving on, though, and it's a big fat book.
I think this lines up with my experience. The way chemistry is often taught its very abstract, borderline magical.
I also had an amazing physics professor who was able to tie literally everything we learned back to real practical and observable events. There is an art to teaching these subjects. This is all undergrad level though, and it wasn’t my major.
Yes and no. It depends which branch of chemistry you world have chosen to go down. Physical Chemistry certainly improves a fair amount of the hand waving, but even there the underlying physics is simplified fairly often (as I understand it — I went straight Physics and dabbled in Chemistry from the other side).
As a chemical engineer, one of the signs of maturity was myself and each of my classmates individually coming to accept and embrace the inevitable “magic coefficient”.
The curious always wanted to know why some magic coefficient was there. Where did it come from? How is it measured / calculated? How to derive the magic coefficient?
Eventually you learn that it’s turtles all the down. You can pick apart the magic coefficient and dive into the nuanced physics that its derived from…but then you still end up with a new magic coefficient.
So eventually, the curious students learn that the mysteries are out there for when you want to go out and explore them. But otherwise, we pick our level of abstraction for the problem we’re currently working on and accept the magic coefficients that apply to that level of abstraction.
The real trick is knowing the conditional boundaries when those magic coefficients no longed apply and you either need different ones or “here be dragons”.
Are "magic coefficients" not just a result of the units you are using? Like how h-bar is 1 if you are using natural units
Not in undergraduate chemistry at least. Maybe chem majors had it different. Organic chemistry 1 was basically rote memorization of various reactions and catalysts and their required conditions. Exam questions would be some organic molecule start and some organic molecule end result and you'd have to draw out each and every intermediary step to get to that end result. Organic chemistry 2 was exactly the same just more reactions to memorize. Biochem was a little easier since the exams didn't ask for full pathways but still pretty much pure memorization.
I hated these sorts off classes, where if you had your notes with you, you'd ace the exam and be able to explain everything. Passing or failing depended not on understanding, but simply whether you cram all the specifics and covered edge cases all into your head at once, given the rest of your present courseload preventing you from actually digging in to the best you could. Wrong answers didn't come from not knowing how to solve something, but not remembering exactly how to solve something.
You had a poor organic course. Even orgo 1 should have you thinking about resonance + electron-rich or -deficient areas of molecules and how those lead to reactions.
Of course we talked about those. But if you went off only those you'd miss the edge cases and gotchas the prof laid for you in step 8 of the synthesis. Couldn't get around just doing worksheet after worksheet after worksheet of reactions to try and drive it into your head. Going to office hours to beg for more practice reactions. Everyone scheduled the rest of their major around when they would have to take ochem to make sure the rest of it was as light as possible. Uncurved class averages would be in the 50s.
I was lucky enough to have Morrison and Boyd as my undergrad ochem textbook. they built the material up really well from first principles.
And people clutch their pearls at ai not really understanding anything when people describe university experiences and lessons like this...
Pi and sigma bonds fall out of thinking of it from a physical/symmetrical/statistical perspective. There's not too much hand waving in the modeling of atomic and molecular orbitals.
Yes its like cooking or music. You start just by learning whats in the kitchen and on repeating steps. This creates latent or tacit knowledge that helps with the Why questions down the road.
The physics that predicts chemistry is about 100 years old. Almost nothing people study up to high-school is that recent, and that modern physics tends to be really hard.
> physics that predicts chemistry
Do we have this?
Yes but ... after a few not so mild assumptions, it takes exponential time to solve it. In this case, you need 6 electrons in 2x5 orbitals for the Carbon and 82 electrons and 2x43 orbitals for Bismuth- (perhaps more, I usually work with lighter atom). So now the free parameter are Combinatoric(96,88)~=3E13 and you must construct a matrix of [3E13 x 3E13] and then find the minimal eigenvalue. So you must make a lot of simplifications and more assumptions to get the result before the universe dies.
And this is for a very cold isolated molecule like in this experiment. If you have many moving molecules surrounded by a lot of water molecules at a usual room temperature, it gets much much much worse.
You know that people simulate chemistry on computers, right?
Yes. We also simulate cosmology and quantum systems and play Sims.
this was my experience as well. "here's a trend, it's not true in these cases for reasons we won't explain." I only had two semesters and the second was much better than the first.
that's because chemistry is heavily involved in describing the nature of how elements and molecules interact with each other. There has to be some element of understanding that nothing is quite as clear because we use experiments and their conclusions to slowly but surely eliminate some theories while keeping others until disproven.
Granted I took AP Chem 20 years ago, but I don't remember those names (sigma and pi bonds) being covered at all. (I got a 5 on the test, for what it's worth.)
They are not covered in AP chemistry this is just your typical "when I studied differential geometry in high school" HN comment
they are featured in collegeboard's course and exam description: https://apcentral.collegeboard.org/media/pdf/ap-chemistry-co...
I also took it 20 years ago but I feel like they were (of course I also did undergrad chem 16 years ago so I may be conflating things). It's difficult to explain isomers without explaining why multiple bonds don't rotate.
Wait... wasn't it already understood that relativity influences electron orbits of heavy elements? I clearly remember being taught some of this in physics, in the mid-noughties.
For instance, we know that gold gets its color from relativistic effects.
https://physics.aps.org/articles/v10/s3
Seems to be the first time this was confirmed via direct experimental observation of the orbitals:
Yes: the article says "since the 70s"
The Dirac equation which is the equation for describing the wavelike behavior of electrons. It predicted the existence of antimatter and particle spin.
You start with the Schrödinger equation, add relativity to get the Klein-Gordon equation which is a mess because it's second order in time involving negative probabilities, if you in ways "take the square root" of it you get the Dirac equation.
Relativity has been part of the understanding of electrons since 1928.
https://en.wikipedia.org/wiki/Dirac_equation
I don’t get it, someone explain? Doesn’t everything get color from relativistic effects?
There's even a Wikipedia page for it https://en.wikipedia.org/wiki/Relativistic_quantum_chemistry
Gold electrons at inner orbits travel at a large fraction of the speed of light, which is why gold isn't a silver color. That is really neat.
For context: this is one more experimental confirmation of Dirac's equations (incorporating special relativity into quantum physics).
Very cool.
The paper PDF: https://bpb-us-w2.wpmucdn.com/sites.brown.edu/dist/0/196/fil...
Relativity is also responsible for a lot of weird behaviors of heavy elements, such as the color of gold. Or that lead is a good material for batteries.