Through new experiments, researchers in Switzerland have tested models of how microwaves affect low-temperature chemical reactions between ions and atoms. Through their innovative setup, Valentina Zhelyazkova and colleagues at ETH Zurich showed for the first time how the application of microwave pulses can slow down reaction rates via nonthermal mechanisms.
Physicists have been studying chemical reactions between ions and neutral molecules for some time. At close to room temperature, classical models can closely predict how the electric fields emanating from ions will induce dipoles in nearby neutral molecules, allowing researchers to calculate these reaction rates with impressive accuracy. Yet as temperatures drop close to absolute zero, a wide array of more complex effects come into play, which have gradually been incorporated into the latest theoretical models.
“At low temperatures, models of reactivity must include the effects of the permanent electric dipoles and quadrupole moments of the molecules, the effect of their vibrational and rotational motion,” Zhelyazkova explains. “At extremely low temperatures, even the quantum-mechanical wave nature of the reactants must be considered.”
Rigorous experiments
Although these low-temperature models have steadily improved in recent years, the ability to put them to the test through rigorous experiments has so far been hampered by external factors.
In particular, stray electric fields in the surrounding environment can heat the ions and molecules, so that any important quantum effects are quickly drowned out by noise. “Consequently, it is only in the past few years that experiments have provided information on the rates of ion–molecule reactions at very low temperatures,” Zhelyazkova explains.
In their study, Zhelyazkova’s team improved on these past experiments through an innovative approach to cooling the internal motions of the molecules being heated by stray electric fields. Their experiment involved a reaction between positively-charged helium ions and neutral molecules of carbon monoxide (CO). This creates neutral atoms of helium and oxygen, and a positively-charged carbon atom.
To initiate the reaction, the researchers created separate but parallel supersonic beams of helium and CO that were combined in a reaction cell. “In order to overcome the problem of heating the ions by stray electric fields, we study the reactions within the distant orbit of a highly excited electron, which makes the overall system electrically neutral without affecting the ion–molecule reaction taking place within the electron orbit,” explains ETH’s Frédéric Merkt.
Giant atoms
In such a “Rydberg atom”, the highly excited electron is some distance from the helium nucleus and its other electron. As a result, a Rydberg helium atom can be considered an ion with a “spectator” electron, which has little influence over how the reaction unfolds. To ensure the best possible accuracy, “we use a printed circuit board device with carefully designed surface electrodes to deflect one of the two beams,” explains ETH’s, Fernanda Martins. “We then merged this beam with the other, and controlled the relative velocity of the two beams.”
Altogether, this approach enabled the researchers to cool the molecules internally to temperatures below 10 K – where their quantum effects can dominate over externally induced noise. With this setup, Zhelyazkova, Merkt, Martins, and their colleagues could finally put the latest theoretical models to the test.
According to the latest low-temperature models, the rate of the CO–helium ion reaction should be determined by the quantized rotational states of the CO molecule – whose energies lie within the microwave range. In this case, the team used microwave pulses to put the CO into different rotational states, allowing them to directly probe their influence on the overall reaction rate.
Three important findings
Altogether, their experiment yielded three important findings. It confirmed that the reaction rate can vary, depending on the rotational state of the CO molecule; it showed that this reactivity can be modified by using a short microwave pulse to excite the CO molecule from its ground state to its first excited state – with the first excited state being less reactive than the ground state.
The third and most counterintuitive finding is that microwaves can slow down the reaction rate, via mechanisms unrelated to the heat they impart on the molecules absorbing them. “In most applications of microwaves in chemical synthesis, the microwaves are used as a way to thermally heat the molecules up, which always makes them more reactive,” Zhelyazkova says.
Building on the success of their experimental approach, the team now hopes to investigate these nonthermal mechanisms in more detail – with the aim to shed new light on how microwaves can influence chemical reactions via effects other than heating. In turn, their results could ultimately pave the way for advanced new techniques for fine-tuning the rate of reactions between ions and neutral molecules.
The research is described in Physical Review Letters.
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