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This paper concerns the analysis of large quantum states. It is a notoriously difficult problem to quantify separability of quantum states, and for large quantum states, it is unfeasible. Here we posit that when quantum states are large, we can deduce reasonable expectations for the complex structure of non-classical multipartite correlations with surprisingly little information about the state. We show, with pegagogical examples, how known results from combinatorics can be used to reveal the expected structure of various correlations hidden in the ensemble described by a state. 

Recent work has exposed the idea that interesting quantum-like (QL) probability laws, including interference effects, can be manifest in classical systems. Here, we propose a model for QL states and QL bits. We suggest a way that huge, complex systems can host robust states that can process information in a QL fashion. Axioms that such states should satisfy are proposed. Specifically, it is shown that building blocks suited for QL states are networks, possibly very complex, that we defined based on $k$-regular random graphs. These networks can dynamically encode a lot of information that is distilled into the emergent states we can use for QL processing. Although the emergent states are classical, they have properties analogous to quantum states. Concrete examples of how QL functions are possible are given. The possibility of a ‘QL advantage’ for computing-type operations and the potential relevance for new kinds of function in the brain are discussed and left as open questions. 

Conspectus: The role of quantum mechanical coherences or coherent superposition states in excited state processes has received considerable attention in the last two decades largely due to advancements in ultrafast laser spectroscopy. These coherence effects hold promise for enhancing the efficiency and robustness of functionally relevant processes, even when confronted with strong energy disorder and environmental fluctuations. Understanding coherence deeply drives us to unravel mechanisms and dynamics controlled by order and synchronization at a quantum mechanical level, envisioning optical control of coherence to enhance functions or create new ones in molecular and material systems. In this frontier, the interplay between electronic and vibrational dynamics, specifically the influence of vibrations in directing electronic dynamics, has emerged as the leading principle. Here, two energetically disparate quantum degrees of freedom work in-sync to dictate the trajectory of an excited state reaction. Moreover, with the vibrational degree being directly related to the structural composition of molecular or material systems, new molecular designs could be inspired by tailoring certain structural elements. In the realm of chemical kinetics, our understanding of the dynamics of chemical transformations is underpinned by fundamental theories such as transition state theory, activated rate theory, and Marcus theory. These theories elucidate reaction rates by considering the energy barriers that must be overcome for reactants to transform into products. Those barriers are surmounted by the stochastic nature of energy gap fluctuations within reacting systems, emphasizing that the reaction coordinate—the pathway from reactants to products—is not rigidly defined by a specific vibrational motion but encompasses a diverse array of molecular motions. While less is known about the involvement of specific intramolecular vibrational modes, their significance in certain cases cannot be overlooked. In this Account, we summarize key experimental findings that offer deeper insights into the complex electronic-vibrational trajectories encompassing excited states afforded from state-of-the-art ultrafast laser spectroscopy in three exemplary processes: photo-induced electron transfer, singlet-triplet intersystem crossing, and intramolecular vibrational energy flow in molecular systems. We delve into rapid decoherence—loss of phase and amplitude correlations—of vibrational coherences along promoter vibrations during a sub-picosecond intersystem crossing dynamics in a series of binuclear platinum complexes. This rapid decoherence illustrates the vibration-driven reactive pathways from Franck-Condon state to the curve crossing region. We also explore the generation of new vibrational coherences induced by impulsive reaction dynamics—rather than by the laser pulse—in these systems, which sheds light on specific energy dissipation pathways and thereby on the progression of the reaction trajectory in the vicinity of the curve crossing on the product side. Another property of vibrational coherences, amplitude, reveals how energy can flow from one vibration to another in the electronic excited state of a terpyridine-molybdenum complex hosting a nonreactive dinitrogen substrate. A slight change in vibrational energy triggers a quasi-resonant interaction, leading to constructive wavepacket interference and ultimately intramolecular vibrational redistribution from a Franck-Condon active terpyridine vibration to dinitrogen stretching vibration, energizing the dinitrogen bond. 

Some of the fundamentals of quantum information science are described, including the concepts of quantum resources, quantum states and mixedness of states. The explanations are detailed and include a combination of basic facts with fully worked examples, and some more advanced topics. The principles of quantum information are illustrated with chemical examples drawn from singlet fission, photophysics of radicals, molecular excitons, electron transfer and so on. Suggestions for prospects and challenges for the field are discussed. 

The present work is motivated by the need for robust, large-scale coherent states that can play possible roles as quantum resources. A challenge is that large, complex systems tend to be fragile. However, emergent phenomena in classical systems tend to become more robust with scale. Do these classical systems inspire ways to think about robust quantum networks? This question is studied by characterizing the complex quantum states produced by mapping interactions between a set of qubits from structure in graphs. We focus on maps based on k-regular random graphs where many edges were randomly deleted. We ask how many edge deletions can be tolerated. Surprisingly, it was found that the emergent coherent state characteristic of these graphs was robust to a substantial number of edge deletions. The analysis considers the possible role of the expander property of k-regular random graphs.