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A theoretical study of the non‐radiative photophysical relaxation mechanisms of the first singlet excited state of benzene, cyclobutadiene and fulvene is presented. For these molecules, the calculation of the Minimum Energy Path (MEP) leading from the Franck–Condon region to the surface crossing with the ground state is carried out. Subsequently, the decomposition of the electronic energies into atomic and pair contributions is performed using the Interacting Quantum Atom (IQA) method. The IQA approach provides the important mechanistic information necessary to rationalise some relevant aspects of the processes, such as the components that explain the appearance of an energy barrier or that favour the crossing between potential energy surfaces (PES); it also allows to quantify the direct effect on the MEP due to the inclusion of a substituent. In particular, it is shown how the IQA energies allow measuring the extent to which the formation of biradicaloid structures affects the crossing of the PES. The analysis of electron density functions suggests that aromaticity is not a driving force on the relaxation processes. Overall, this work shows the potential of the IQA method as a useful tool for the detailed description of photophysical processes. [ABSTRACT FROM AUTHOR]

Oxazolones or azlactones are small heterocyclic systems that can be easily functionalized with a double bond directly attached to their structure. In addition, they can be substituted on the opposite side of the heterocycle with styrenyl groups to extend their conjugation. This allows for versatile tuning of their linear and non‐linear optical properties. In this work, eight doubly substituted oxazolones including different push‐pull or pull‐pull designs were synthesized, and their linear and non‐linear photophysical properties were studied. As we show, the two‐photon activity of these systems is dependent on the donor‐acceptor pattern, where a methoxy substitution on the styrene end of the molecule and an acetyl group on the other end shows two‐photon Z‐E conversion properties with an important two photon absorption cross section of 308 GM. Most oxazolones shown in this study undergo picosecond relaxation to the electronic ground state, releasing the biphotonic energy to their surrounding environment. The results obtained in this work are indicative of potential applications of these molecules in schemes where high spatial patterning or thermalization is required. [ABSTRACT FROM AUTHOR]

A number of aromatic, antiaromatic, and nonaromatic organic molecules was analyzed in terms of the contributions to the electronic energy defined in the quantum theory of atoms in molecules and the interacting quantum atoms method. Regularities were found in the exchange and electrostatic interatomic energies showing trends that are closely related to those of the delocalization indices defined in the theory. In particular, the CC interaction energies between bonded atoms allow to rationalize the energetic stabilization associated with the bond length alternation in conjugated polyenes. This approach also provides support to Clar's sextet rules devised for aromatic systems. In addition, the H ⋯H bonding found in some of the aromatic molecules studied was of an attractive nature, according to the stabilizing exchange interaction between the bonded H atoms. © 2017 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

Real-space tools were employed to show that the chemical bonding scenario used routinely to understand ground states lacks the necessary flexibility in excited states. It is shown that, even for two-center, two-electron bonds, the real-space bond orders have exotic values that have never been reported. The nature of these situations was uncovered by using electron-counting techniques that provide an appealing statistical interpretation of bonding descriptors, together with simple physical models. Bond orders greater than one as well as negative bond orders for a single bonding electron pair emerge in situations in which the electrons in the pair show a gregarious (bosonic) instead of the usual lonely (fermionic) behavior. In the first case the gregarious pair is intra-atomic, whereas the coupling is interatomic in the second. A number of examples are used to substantiate these claims., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)