One of the most successful uses of quantum mechanical modeling methods is to predict spectra. These methods are capable of yielding good predictions of UV/Visible, NMR, Infrared, Raman, THz, and EELS (electron energy loss spectroscopy) to name just a few. Spectroscopy (according to Wikipedia) is the “study of the interaction between radiation and matter as a function of wavelength … or frequency.” How does this help chemists? We can use the spectra to determine the structure of new molecules or materials; to determine the composition of mixtures; or to follow the course of a chemical reaction in situ. How does modeling help with this? In a number of ways, but I’ll cover just 2.
One way modeling comes into play is by working with experimental results to remove ambiguities. When a chemist is trying the determine the structure of a new material, he or she takes a spectrum, or two, or three. His or her knowledge of the ingredients together with the spectra gives a pretty good idea what the chemical or crystal structure is. In a lot of cases the data are sufficient only to narrow this down to 3-4 possible structures. Molecular modeling resolve this ambiguity by predicting the spectrum of each possibility; the spectrum that matches the experimental one presumably corresponds to the “right” one. Modeling is even more valuable when investigating defect structures like this work on Mg2.5VMoO8.
Another use is telling where experimentalists to look for the spectral peaks of a new compound. This can be especially important when trying to detect the spectra of new, novel, or poorly characterized materials. Experimental terahertz (THz) spectroscopy, for example, examines the spectral range of 3-120 cm-1, and can be used for detection and identification for a wide assortment of compounds including explosives like HMX. It’s a lot safer to investigate these materials by modeling than in the lab.
A recent blog by Dr. Damian Allishighlights the importance of doing the simulations correctly. (By the way, Damian, congrats on getting to page 1000.) A lot of work for the past 40-odd years has gone into predicting spectra of isolated – or gas phase – molecules. But materials like HMX are crystalline, and calculations on the isolated molecules make for poor comparison with crystals. The recent work underscores how important it is to simulate crystals using crystals. And it’s not just for THz spectra. Recent work on NMR leads to the same conclusion. A couple of programs can do this. Damian’s blog focuses on DMol3 and Crystal06, but we should also mention CASTEP and Gaussian as other applications capable of predicting a wide variety of properties for solids.
Let’s keep modeling – but be careful out there: short cuts will lead to poor results, and molecular modeling will end up taking the rap for user error.
