Chemical chameleon tamed: Researchers give floppy molecule a structure through solvent effects

March 14, 2013
Giving the “chameleon molecule" structure: Depending on how many H2 solvent molecules (blue) attach to the CH5+ molecule, the area in which the hydrogen atoms of the CH5+ molecule move changes (red). Its structure is thus partially “frozen”. The areas represent quantum mechanical probability densities at a temperature of 20 Kelvin. Credit: A. Witt, S. Ivanov, D. Marx

How you get the chameleon of the molecules to settle on a particular "look" has been discovered by RUB chemists led by Professor Dominik Marx. The molecule CH5+ is normally not to be described by a single rigid structure, but is dynamically flexible. By means of computer simulations, the team from the Centre for Theoretical Chemistry showed that CH5+ takes on a particular structure once you attach hydrogen molecules. "In this way, we have taken an important step towards understanding experimental vibrational spectra in the future", says Dominik Marx.

The researchers report in the journal Physical Review Letters.

In the CH5+ molecule, the hydrogen atoms are permanently on the move

The superacid CH5+, also called protonated methane, occurs in outer space - where new stars are formed. Researchers already discovered the molecule in the 1950s, but many of its features are still unknown. Unlike conventional molecules in which all the atoms have a fixed position, the five in CH5+ are constantly moving around the carbon centre. Scientists speak of "hydrogen scrambling". This dynamically flexible structure has been explained by the research groups led by Dominik Marx and Stefan Schlemmer of the University of Cologne as part of a long-term collaboration (reported in July 2005 and March 2010). Marx's team now wanted to know if the structure can be "frozen" under certain conditions by attaching solvent molecules – a process called microsolvation.

Microsolvatation: addition of hydrogen molecules to CH5+ one by one

To this end, the chemists surrounded the CH5+ molecule in the virtual lab with a few hydrogen molecules (H2). Here, the result is the same as when dissolving normal ions in water: a relatively tightly bound shell of attaches to each ion in order to then transfer individual ions with several solvent molecules bound to them to the . To describe the CH5+ hydrogen complexes, classical ab initio molecular dynamics simulations are not sufficient. The reason is that "hydrogen scrambling" is based on quantum effects. Therefore Marx's group used a fully quantum mechanical method which they developed in house, known as ab initio path integral simulation. With this, the essential quantum effects can be taken into account dependent on the temperature.

Hydrogen molecules give the CH5+ molecule "structure"

The chemists carried out the simulations at a temperature of 20 Kelvin, which corresponds to -253 degrees Celsius. In the non-microsolvated form, the five hydrogen atoms in the CH5+ molecule are permanently changing positions even at such low temperatures – and entirely due to quantum mechanical effects. If CH5+ is surrounded by hydrogen molecules, this "hydrogen scrambling" is, however, significantly effected and may even completely come to a halt: the molecule assumes a rudimentary structure. How this looks exactly depends on how many hydrogen molecules are attached to the CH5+ molecule. "What especially interests me is if superfluid helium – like the here – can also stop hydrogen scrambling in CH5+" says Marx. Experimental researchers use superfluid helium to measure high-resolution spectra of molecules embedded in such droplets. For CH5+ this has so far not been possible. In the superfluid phase, the helium atoms are, however, indistinguishable due to quantum statistical effects. To be able to describe this fact, the theoretical chemists at the RUB spent many years developing a new, even more complex path-integral-based simulation method that has recently also been applied to real problems.

Explore further: Formation of the smallest droplet of acid

More information: Witt, A., Ivanov, S. and Marx, D. (2013): Microsolvation-Induced Quantum Localization in Protonated Methane, Physical Review Letters, doi: 10.1103/PhysRevLett.110.083003

Related Stories

Formation of the smallest droplet of acid

June 19, 2009

Exactly four water molecules and one hydrogen chloride molecule are necessary to form the smallest droplet of acid. This was the result of work by the groups of Prof. Dr. Martina Havenith (physical chemistry) and Prof. Dr. ...

An unexpected pairing of frustrated molecules

January 21, 2013

While their shapes frustrate traditional bonding, two unreactive molecules come together and surround themselves within a solvent cage to create a reactive environment and split hydrogen.

Recommended for you

Findings illuminate animal evolution in protein function

July 27, 2015

Virginia Commonwealth University and University of Richmond researchers recently teamed up to explore the inner workings of cells and shed light on the 400–600 million years of evolution between humans and early animals ...

New polymer able to store energy at higher temperatures

July 30, 2015

(Phys.org)—A team of researchers at the Pennsylvania State University has created a new polymer that is able to store energy at higher temperatures than conventional polymers without breaking down. In their paper published ...

How to look for a few good catalysts

July 30, 2015

Two key physical phenomena take place at the surfaces of materials: catalysis and wetting. A catalyst enhances the rate of chemical reactions; wetting refers to how liquids spread across a surface.

Yarn from slaughterhouse waste

July 29, 2015

ETH researchers have developed a yarn from ordinary gelatine that has good qualities similar to those of merino wool fibers. Now they are working on making the yarn even more water resistant.

0 comments

Please sign in to add a comment. Registration is free, and takes less than a minute. Read more

Click here to reset your password.
Sign in to get notified via email when new comments are made.