Electronic Coherences Excited by an Ultra Short Pulse Are Robust with Respect to Averaging over Randomly Oriented Molecules as Shown by Singular Value Decomposition.

We report a methodology for averaging quantum photoexcitation vibronic dynamics over the initial orientations of the molecules with respect to an ultrashort light pulse. We use singular value decomposition of the ensemble density matrix of the excited molecules, which allows the identification of the few dominant principal molecular orientations with respect to the polarization direction of the electric field. The principal orientations provide insights into the specific stereodynamics of the corresponding principal molecular vibronic states. The massive compaction of the vibronic density matrix of the ensemble of randomly oriented pumped molecules enables a most efficient fully quantum mechanical time propagation scheme. Two examples are discussed for the quantum dynamics of the LiH molecule in the manifolds of its electronically excited Σ and Π states. Our results show that electronic and vibrational coherences between excited states of the same symmetry are resilient to averaging over an ensemble of molecular orientations and can be selectively excited at the ensemble level by tuning the pulse parameters.

Correction: Bond breaking of furan-maleimide adducts via a diradical sequential mechanism under an external mechanical force.

[This corrects the article DOI: 10.1039/D2SC05051J.].

Bond breaking of furan-maleimide adducts via a diradical sequential mechanism under an external mechanical force.

Substituted furan-maleimide Diels-Alder adducts are bound by dynamic covalent bonds that make them particularly attractive mechanophores. Thermally activated [4 + 2] retro-Diels-Alder (DA) reactions predominantly proceed via a concerted mechanism in the ground electronic state. We show that an asymmetric mechanical force along the anchoring bonds in both the endo and exo isomers of proximal dimethyl furan-maleimide adducts favors a sequential pathway. The switching from a concerted to a sequential mechanism occurs at external forces of ≈1 nN. The first bond rupture occurs for a projection of the pulling force on the scissile bond at ≈4.3 nN for the exo adduct and ≈3.8 nN for the endo one. The reaction is inhibited for external forces up to ≈3.4 nN for the endo adduct and 3.6 nN for the exo one after which it is activated. In the activated region, at 4 nN, the rupture rate of the first bond for the endo adduct is computed to be ≈3 orders of magnitude larger than for the exo one in qualitative agreement with recent sonication experiments [Z. Wang and S. L. Craig, Chem. Commun., 2019, 55, 12263-12266]. In the intermediate region of the path between the rupture of the first and the second bond, the lowest singlet state exhibits a diradical character for both adducts and is close in energy to a diradical triplet state. The computed values of spin-orbit coupling along the path are too small for inducing intersystem crossings. These findings open the way for the rational design of DA mechanophores for polymer science and photochemistry.