Thursday, 21 May 2015

Twisted Intramolecular Charge Transfer

Admittedly, we are not the only people working on Dimethylaminobenzonitrile (DMABN) and its dual fluoresence. But it is an interesting system worth looking at. Our paper about this topic "Intramolecular Charge Transfer Excited State Processes in 4-(N,N-Dimethylamino)benzonitrile: The Role of Twisting and the πσ* State" is finally released after starting this project about four years ago. Check it out if you are interested.


Friday, 24 April 2015

The 4-Hour Scientist

Tim Ferris' 4-Hour Workweek is the ultimate treatise on how to work less. For most of us in science, eliminating work is not the utmost goal, as many of us like what we are doing. But there are still a number of things we can learn. First, making a dent into the cushion of your office chair is not an end in itself, and there is no reason why you should do this for eight hours every day. And as I would argue not even the number of papers is a good measure for personal success as a scientist. Anyway, whether your goals are to have more free time, to spend time with your family, to train for a sports event, or if you are really just trying to boost your publication list, here are some tips as inspired by the book.

Work less, think more. What we are supposed to do is science, after all.

Automatize. Repetitive things can be programmed. If you don't know how to, take a day off and learn basic bash and python.

Email less. Email is one of the worst time killers and procrastination excuses. Always finish an actual task first before you even think about opening your emails. Then close them really quickly, get back to work, and go home at 4 p.m.

Focus. Pick two tasks for the day, finish them and go home. Eliminate your "task switching costs" and do not give yourself any excuses to drift off.

Prioritize. Work and payoff are not linearly related. As the story goes, 20% of peapods in Pareto's garden produced 80% of the peas. And 80% of your output probably comes from 20% of your work. Find those 20% and eliminate the rest. On the other hand 80% of your sleepless nights may derive from just 20% of your projects - eliminate those as well.

I would argue that focusing on doing important things rather than many things will provide you with an advantageous scientific profile. And eliminating the hopeless tasks may even increase your output. And even if not, it is time to relax. If toiling all day, doing dull things while stressing yourself out is really the only way to get ahead in science, why would you want that?

But is there a moral obligation to work a lot? Am I somehow tricking my sponsors if I don't work "enough"? Well, the dent in my office chair is really not what counts.

Tuesday, 10 March 2015

Löwdin orthogonalization

Did you know that you can do a Löwdin orthogonalization by a singular value decomposition? Usually, when I hear Löwdin orthogonalization, I think of some weird S1/2 matrix, which scares me and I tend to stay away from it... But this pdf from the University of Oregon claims that you can do it in a different way. And it seems to work.

Say you have a matrix A and you want an orthogonal matrix that resembles it as closely as possible. What do you do? First you do a singular value decomposition of A:

Here U and V are orthogonal matrices and Λ is a diagonal matrix. We can now construct
which is an orthogonal matrix, since U and V are both orthogonal matrices. But even more, A' is the orthogonal matrix that best resembles A in the sense that for all orthogonal matrices Q it minimizes the distance with respect to the Frobenius norm

That is all you have to do.

Monday, 16 February 2015

European PhD positions open

If anyone is interested: there are three PhD positions opening up in our group (back in Vienna). These are EU projects where half of the time will be spent in Vienna and the other half in either Pisa, Toulouse, or Madrid.

To learn more, check out the Jobs page of the Gonzalez group. And if you need more information you can of course contact me or write directly to Leticia Gonzalez.

Friday, 30 January 2015

Iridium complexes and the failure of ADC(2) to describe them

When I started working on iridium complexes two and a half years ago, there was one simple thing I could not explain: The results at the ADC(2) level were more than one eV off from the ADC(3) reference. And that is not good: you would not expect that a correlated ab-initio method would fail so badly. What followed was a two year detour through the world of excited state analysis (seen in some previous posts: [1], [2], [3], [4], [5]). And finally, I feel like I am in a position to discuss the above question properly in our new paper "High-Level Ab Initio Computations of the Absorption Spectra of Organic Iridium Complexes", which just appeared in JPCA.



The first step was to properly quantify the charge transferred using population analysis schemes. This revealed that ADC(2) had a strong bias toward overstabilizing charge transfer states. Usually you would think that this is a problem of TDDFT. But interestingly even TDDFT/B3LYP performed much better with errors only on the order of 0.5 eV.

To quantify the problem of ADC(2) we needed a new tool. For this purpose we took a closer look at the attachment/detachment analysis of Head-Gordon. While it is common to visualize the attachment and detachment densities, there is also an important meaning to the integral over them, the promotion number p. This quantity counts the total number of rearranged electrons and proved as a useful measure for orbital relaxation effects, which are difficult to understand otherwise.

So what happened when we made this analysis? At the ADC(1) level (whose energies and state densities are identical to CIS) p has to be equal to 1 per construction. Then ADC(2) apparently overestimates orbital relaxation effects with p values above 1.5. And only the ADC(3) level is balanced enough to cover some but not too much orbital relaxation.