A recent
development in quantum chemistry has established the quantum
mutual information between orbitals as a major descriptor of electronic
structure. This has already facilitated remarkable improvements in
numerical methods and may lead to a more comprehensive foundation
for chemical bonding theory. Building on this promising development,
our work provides a refined discussion of quantum information theoretical
concepts by introducing the physical correlation and its separation
into classical and quantum parts as distinctive quantifiers of electronic
structure. In particular, we succeed in quantifying the entanglement.
Intriguingly, our results for different molecules reveal that the
total correlation between orbitals is mainly classical, raising questions
about the general significance of entanglement in chemical bonding.
Our work also shows that implementing the fundamental particle number
superselection rule, so far not accounted for in quantum chemistry,
removes a major part of correlation and entanglement seen previously.
In that respect, realizing quantum information processing tasks with
molecular systems might be more challenging than anticipated.
In this work, we study singlet fission in tetracene para-dimers, covalently linked by a phenyl group. In contrast to most previous studies, we account for the full quantum dynamics of the combined excitonic and vibrational system. For our simulations, we choose a numerically unbiased representation of the molecule’s wave function, enabling us to compare with experiments, exhibiting good agreement. Having access to the full wave function allows us to study in detail the post-quench dynamics of the excitons. Here, one of our main findings is the identification of a time scale t0 ≈ 35 fs dominated by coherent dynamics. It is within this time scale that the larger fraction of the singlet fission yield is generated. We also report on a reduced number of phononic modes that play a crucial role in the energy transfer between excitonic and vibrational systems. Notably, the oscillation frequency of these modes coincides with the observed electronic coherence time t0. We extend our investigations by also studying the dependency of the dynamics on the excitonic energy levels that, for instance, can be experimentally tuned by means of the solvent polarity. Here, our findings indicate that the singlet fission yield can be doubled, while the electronic coherence time t0 is mainly unaffected.
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