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New Scientist3 days ago
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Special relativity can warp chemical bonds – now we’ve seen it happen

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Researchers observed special relativity warping chemical bonds in a bismuth-carbon molecule for the first time, confirming that relativistic effects can alter bond types.

Special relativity can warp chemical bonds – now we’ve seen it happen

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The Big Picture
A team led by Lai-Sheng Wang at Brown University used a cold molecule experiment to map electron distributions in a bismuth-carbon molecule, expecting standard sigma and pi bonds. Instead, they found two bonds that were mixtures of sigma and pi shapes, which calculations by Kirk Peterson at Washington State University attributed to relativistic speeds of electrons near the bismuth nucleus. This is the first experimental capture of special relativity directly affecting chemical bonds, an effect previously only theorized for heavy elements. The finding has implications for understanding bonding in heavy elements like bismuth, gold, and mercury, and may influence the use of bismuth compounds as catalysts. The team plans to repeat the experiment with nearby elements to explore the threshold where relativistic effects dominate.
Why It Matters
This experiment provides the first direct evidence that special relativity can alter chemical bonds in heavy elements, challenging the standard sigma/pi bond model. The findings have practical implications for catalysis, as relativistic effects in bismuth compounds can enhance their performance as catalysts, potentially leading to more efficient industrial chemical processes. It also underscores the need to incorporate relativity into quantum chemistry for heavy elements, which could reshape our understanding of the periodic table's lower rows.

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In some heavy atoms, like those of bismuth (pictured in crystalline form), electrons move at relativistic speedssavva_25/Shutterstock

Albert Einstein’s theory of special relativity can reshape chemical bonds within molecules, and researchers have just seen it happen for the first time.

The theory of special relativity describes how moving at speeds close to the speed of light would affect travellers’ experience of space and time. Because of this, it is usually associated with particle accelerators and spacefaring objects, but within some heavy atoms, electrons experience relativistic speeds too.

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Chemists discovered the first new chemical bond in more than a decade

Lai-Sheng Wang at Brown University in Rhode Island and his colleagues have now managed to take an unprecedented look at how this breaks the standard notion of chemical bonds within a charged molecule made from bismuth and carbon.

Within the molecule, a bismuth atom and a carbon atom were connected by three bonds, one of which the researchers expected to be of “sigma” type and two of “pi” type. The difference between these two types stems from electrons’ quantum character – each electron is “smeared” across some region of space, instead of being a tight ball, and whether these regions overlap head on or side by side determines the type of chemical bond they create between the atoms.

In their experiment, Wang and his colleagues mapped the distribution of electrons throughout the molecule, effectively getting a look at its bonds. But instead of seeing electrons distributed in shapes associated with sigma and pi bonds, the team noticed that two of the bonds resembled two different mixes of sigma and pi shapes. “Their characters are different from our normal understanding,” says Wang. “You can’t really call it the sigma and pi.”

His team turned to Kirk Peterson at Washington State University, whose calculations ultimately showed that this mixing was a consequence of electrons near the bismuth nucleus feeling such a strong electromagnetic interaction that they moved at relativistic speeds. He says this effect hadn’t previously been captured in an experiment.

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“The hardest thing about [studying] heavy elements is a lack of really good experimental data,” says Peterson. “To have such a beautiful experiment to be able to essentially compare very high-level theory to data is really a luxury.”

Wang says one important part of the new experiment is that he and his colleagues could make the molecule very cold before looking at its electrons. This dampened any jitters and excitations that would have made the final images imprecise.

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A new version of the periodic table could change how we measure time

“As you go down to the bottom of the periodic table, the usual quantum mechanics is no longer sufficient, you need to take into account the effects of relativity,” says Trond Saue at the University of Toulouse in France. He says that all elements in the same row of the periodic table as bismuth are affected by relativistic effects – for instance, gold would be the same colour as silver and mercury would not be liquid without them.

Pekka Pyykkö at the University of Helsinki in Finland says that for bismuth, the relativistic effect on its bonding with carbon could influence how organic bismuth compounds are used in chemical reactions. In fact, a recent study by researchers at the Max Planck Institute for Coal Research in Germany has already shown that relativistic effects help make this heavy metal a good catalyst, or accelerator, of chemical processes.

Wang says that the team now wants to repeat their experiment but swap bismuth for elements close to it in the periodic table to see when exactly special relativity makes the traditional chemical bond structure collapse.

Journal reference:

Science DOI: 10.1126/science.aei1285

Science Physics Chemistry Quantum Mechanics Relativity

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