Sunday, July 8, 2018

Square ice on graphene?

As I have written many times before, water is fascinating, a rich source of diverse and unusual phenomena, and an unfortunate source of spurious research reports.
Polywater is the classic example of the latter.
I find the physics particularly interesting because of the interplay of hydrogen bonding and quantum nuclear effects such as zero-point motion and tunneling.

There is a fascinating paper
Polymorphism of Water in Two Dimensions
Tanglaw Roman and Axel GroƟ

The paper was stimulated by a Nature paper that claimed to experimentally observe square ice inside graphene nanocapillaries. Such a square structure is in contrast to the hexagonal structure found in regular three-dimensional ice.
Subsequent, theoretical calculations claimed to support this observation of square ice.
Here the authors use DFT-based methods to calculate the relative energies of a range of two-dimensional structures for free-standing sheets of water (both single layer and bilayers) and for sheets bounded by two layers of graphene.

The figure below summarises the authors results for free-standing layers showing how the relative stability of the different water structures depends on the area density of water molecules [which varies the length and strength of the hydrogen bonds].

On the science side, there are several interesting questions arise.
How much do the results depend on the choice of DFT functional used [RPBE with dispersion corrections]?
Would inclusion of the nuclear zero-point energy modify the relative stability of some of the structures, as it does for the water hexamer?
Quantum nuclear effects are particularly important when the hydrogen bond length [distance between oxygen atoms] is about 2.4 Angstroms. [I am not quite sure what area density this corresponds to for the different structures].

On the sociology side, this paper is another example of a distressingly common progression:
1. A paper in a luxury journal reports an exotic and exciting new result.
2. More papers appear, some supporting and some raising questions about the result.
3. A very careful analysis reported in a solid professional journal shows the original claim was largely wrong. This paper attracts few citations because the community has moved on to the latest exciting new "discovery" reported in a luxury journal.

I thank Tanglaw Roman for helpful discussions about his paper.


  1. Though I too am critical of the hype cycle, I would point out that Nature itself published the most compelling evidence against the original paper, and that the community quickly took notice.

    1. Which specific Nature article are you referring to?

    2. "The observation of square ice in graphene questioned,"

      The authors suggest that the square lattice observed in the electron microscope arises from contaminants from common salts and support their analysis with EELS spectra, notably absent from the original report.

    3. This impurities which is mentioned in Nature paper is an aspect which is extremely important to be addressed. There are thousands of papers and simulations published day in and day out where this impurity aspect is never considered. In the pre neoliberal times chemists and others experimentalists used to purify the compounds and publish. They used to mention even purification methods. For even mathematical modelling majority of the papers would be publish with 99% pure compounds, since one can apply maths only to pure compounds. The beauty of maths and simulations only comes when you use pure (99% or 100% ) compounds.

      This is sadly missing now. Of the shelf chemicals are used in a hurry and in rush expts and simulations are done and published for funds and career enhancement. Very sad state of affairs.

  2. Ig Nobel for claims of square ice ... ?

  3. I wonder what specific actions Nature (and respected journals in general) has concretely implemented in the area of manuscript reviewing to prevent further unhelpful episodes like this?