Multi-configurational second order perturbation theory (CASPT2) has become a very popular method for describing excited-state properties since its development in 1990. To account for systematic errors found in the calculation of dissociation energies, an empirical correction applied to the zeroth-order Hamiltonian, called the IPEA shift, was introduced in 2004. The errors were attributed to an unbalanced description of open-shell versus closed-shell electronic states and is believed to also lead to an underestimation of excitation energies. Here we show that the use of the IPEA shift is not justified and the IPEA should not be used to calculate excited states, at least for organic chromophores. This conclusion is the result of three extensive analyses. Firstly, we survey the literature for excitation energies of organic molecules that have been calculated with the unmodified CASPT2 method. We find that the excitation energies of 356 reference values are negligibly underestimated by 0.02 eV. This value is an order of magnitude smaller than the expected error based on the calculation of dissociation energies. Secondly, we perform benchmark full configuration interaction calculations on 137 states of 13 di- and triatomic molecules and compare the results with CASPT2. Also in this case, the excited states are underestimated by only 0.05 eV. Finally, we perform CASPT2 calculations with different IPEA shift values on 309 excited states of 28 organic small and medium-sized organic chromophores. We demonstrate that the size of the IPEA correction scales with the amount of dynamical correlation energy (and thus with the size of the system), and gets immoderate already for the molecules considered here, leading to an overestimation of the excitation energies. It is also found that the IPEA correction strongly depends on the size of the basis set. The dependency on both the size of the system and of the basis set, contradicts the idea of a universal IPEA shift which is able to compensate for systematic CASPT2 errors in the calculation of excited states.

We show that in polyadenine UV photons are absorbed by excitons localized on up to three adjacent nucleobases.

The formation of cyclobutane thymine dimers is one of the most important DNA carcinogenic photolesions induced by ultraviolet irradiation. The long debated question whether thymine dimerization after direct light excitation involves singlet or triplet states is investigated here for the first time using nonadiabatic molecular dynamics simulations. We find that the precursor of this [2 + 2] cycloaddition reaction is the singlet doubly π²π*² excited state, which is spectroscopically rather dark. Excitation to the bright ¹ππ* or dark ¹nπ* excited states does not lead to thymine dimer formation. In all cases, intersystem crossing to the triplet states is not observed during the simulated time, indicating that ultrafast dimerization occurs in the singlet manifold. The dynamics simulations also show that dimerization takes place only when conformational control happens in the doubly excited state.

Nitronaphthalene derivatives efficiently populate their electronically excited triplet states upon photoexcitation through ultrafast intersystem crossing (ISC). Despite having been studied extensively by time‐resolved spectroscopy, the reasons behind their ultrafast ISC remain unknown. Herein, we present the first ab initio nonadiabatic molecular dynamics study of a nitronaphthalene derivative, 2‐nitronaphthalene, including singlet and triplet states. We find that there are two distinct ISC reaction pathways involving different electronic states at distinct nuclear configurations. The high ISC efficiency is explained by the very small electronic and nuclear alterations that the chromophore needs to undergo during the singlet–triplet transition in the dominating ISC pathway after initial dynamics in the singlet manifold. The insights gained in this work are expected to shed new light on the photochemistry of other nitro polycyclic aromatic hydrocarbons that exhibit ultrafast intersystem crossing.

Most processes triggered by ultraviolet (UV) or visible (vis) light in nature take place in complex biological environments. The first step in these photophysical events is the excitation of the absorbing system or chromophore to an electronically excited state. Such an excitation can be monitored by the UV-vis absorption spectrum. A precise calculation of the UV-vis spectrum of a chromophore embedded in an environment is a challenging task that requires the consideration of several ingredients, besides an accurate electronic-structure method for the excited states. Two of the most important are an appropriate description of the interactions between the chromophore and the environment and accounting for the vibrational motion of the whole system. In this contribution, we review the most common theoretical methodologies to describe the environment (including quantum mechanics/continuum and quantum mechanics/molecular mechanics models) and to account for vibrational sampling (including Wigner sampling and molecular dynamics). Further, we illustrate in a series of examples how the lack of these ingredients can lead to a wrong interpretation of the electronic features behind the UV-vis absorption spectrum.