New Perspectives on an Old Issue: A Comparative MS-CASPT2 and OM2-MRCI Study of Polyenes and Protonated Schiff Bases

Polyenic systems are involved in light perception of numerous living organisms. Although a π-conjugated backbone is a common feature of all polyenes, their photophysics may vary. We provide a comparative quantum mechanical study of low-lying S₁ and S₂ excited states in short (3-5 double bonds) symmetric all-trans linear polyenes and corresponding protonated Schiff bases. In our investigation, we use the well-established ab initio multireference CASPT2 approach and benchmark the efficient semiempirical OM2-MRCI approach against it. For all protonated Schiff bases, MS-CASPT2 results in two distinct S₁ minima with inverted and noninverted bond length pattern, respectively. We find that OM2-MRCI is a computationally affordable and reliable alternative to MS-CASPT2 for investigations of polyenic systems, particularly when highly demanding calculations (e.g. excited-state dynamics) need to be performed.