Organic chemists often think in terms of potential energy surfaces, especially when plotting the results of a computational study. Unfortunately it is non-trivial to generate high-quality potential energy surfaces.

Now that our work on screening for generality has finally been published in Nature , I wanted to first share a few personal reflections and then highlight the big conclusions that I gleaned from this project. This project originated from conversations I had with Eugene Kwan back in February 2019, when I was still an undergraduate at MIT.

One common misconception in mechanistic organic chemistry is that reactions are accelerated by speeding up the rate-determining step. This mistaken belief can lead to an almost monomaniacal focus on determining the nature of the rate-determining step. In fact, it's more correct to think of reactions in terms of the rate-determining span: the difference between the resting state and the highest-energy transition state.

The growing accessibility of computational chemistry has, unfortunately, led to a preponderance of papers with bad computations.

This is the first in what will hopefully become a series of blog posts focusing on the fascinating work of Dan Singleton (professor at Texas A&M). My goal is to provide concise and accessible summaries of his work and highlight conclusions relevant to the mechanistic or computational chemist. A central theme in mechanistic chemistry is the question of concertedness: if two steps occur simultaneously (“concerted”) or one occurs

As an undergraduate student in the sciences at MIT, contempt for management consulting was commonplace. Consulting was the path for people who had ambition devoid of any real interests, the “sellout road” where you made endless Powerpoints instead of providing any tangible improvement to the world. In contrast, going to graduate school was a choice that showed commitment and integrity.

For many organic chemists, it’s hard to grasp the vast difference between various “fast” units of time. For instance, if a reactive intermediate has a lifetime of microseconds, does that mean it can escape the solvent shell and react with a substrate? What about a lifetime of nanoseconds, picoseconds, or femtoseconds?

While IR spectroscopy is still taught in introductory organic chemistry classes, it has been almost completely replaced by NMR spectroscopy and mass spectrometry for routine structural assignments.

In my experience, most computational chemists only know a handful of basic Bash commands, which is a shame because Bash is incredibly powerful. Although I'm far from an expert, here are a few commands I frequently find myself using: 1. sed For Find-and-Replace. $ sed -i “s/b3lyp/m062x/” *.gjf If you want to resubmit a bunch of transition states at a different level of theory, don't use a complex package like cctk!

This thesis, from Christian Sailer at Ludwig Maximilian University in Munich, is one of the most exciting studies I’ve read this year. Sailer and coworkers are able to generate benzhydryl carbocations from photolysis of the corresponding phosphonium salts, and can monitor their formation and lifetime via femtosecond transient absorption spectroscopy.