Magnetic molecules, modelled as finite-size spin systems, are test-beds for quantum phenomena1 and could constitute key elements in future spintronics devices2–5, long-lasting nanoscale memories6 or ...noise-resilient quantum computing platforms7–10. Inelastic neutron scattering is the technique of choice to probe them, characterizing molecular eigenstates on atomic scales11–14. However, although large magnetic molecules can be controllably synthesized15–18, simulating their dynamics and interpreting spectroscopic measurements is challenging because of the exponential scaling of the required resources on a classical computer. Here, we show that quantum computers19–22 have the potential to efficiently extract dynamical correlations and the associated magnetic neutron cross-section by simulating prototypical spin systems on a quantum hardware22. We identify the main gate errors and show the potential scalability of our approach. The synergy between developments in neutron scattering and quantum processors will help design spin clusters for future applications.Inelastic neutron scattering is used to probe the spin dynamics of molecular nanomagnets, but extensive supporting computations make the technique challenging. Proof-of-principle experiments now show that quantum computers may solve these computations efficiently.
The ultrafast nonadiabatic dynamics of a prototypical Cu(I)–phenanthroline complex, Cu(dmp)2+ (dmp = 2,9-dimethyl-1,10-phenanthroline), initiated after photoexcitation into the optically bright ...metal-to-ligand charge-transfer (MLCT) state (S3) is investigated using quantum nuclear dynamics. In agreement with recent experimental conclusions, we find that the system undergoes rapid (∼100 fs) internal conversion from S3 into the S2 and S1 states at or near the Franck–Condon (FC) geometry. This is preceded by a dynamic component with a time constant of ∼400 fs, which corresponds to the flattening of the ligands associated with the pseudo Jahn–Teller distortion. Importantly, our simulations demonstrate that this latter aspect is in competition with subpicosecond intersystem crossing (ISC). The mechanism for ISC is shown to be a dynamic effect, in the sense that it arises from the system traversing the pseudo Jahn–Teller coordinate where the singlet and triplet states become degenerate, leading to efficient crossing. These first-principles quantum dynamics simulations, in conjunction with recent experiments, allow us to clearly resolve the mechanistic details of the ultrafast dynamics within Cu(dmp)2+, which have been disputed in the literature.
The excited state properties of transition metal complexes have become a central focus of research owing to a wide range of possible applications that seek to exploit their luminescence properties. ...Herein, we use density functional theory (DFT), time-dependent DFT (TDDFT), classical and quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations to provide a full understanding on the role of the geometric and electronic structure, spin–orbit coupling, singlet–triplet gap and the solvent environment on the emission properties of nine prototypical copper(I)–phenanthroline complexes. Our calculations reveal clear trends in the electronic properties that are strongly correlated to the luminescence properties, allowing us to rationalize the role of specific structural modifications. The MD simulations show, in agreement with recent experimental observations, that the lifetime shortening of the excited triplet state in donor solvents (acetonitrile) is not due to the formation of an exciplex. Instead, the solute–solvent interaction is transient and arises from solvent structures that are similar to the ones already present in the ground state. These results based on a subset of the prototypical mononuclear Cu(I) complexes shed general insight into these complexes that may be exploited for development of mononuclear Cu(I) complexes for applications as, for example, emitters in third generation OLEDs.
Understanding chiral-induced spin selectivity (CISS), resulting from charge transport through helical systems, has recently inspired many experimental and theoretical efforts but is still the object ...of intense debate. In order to assess the nature of CISS, we propose to focus on electron-transfer processes occurring at the single-molecule level. We design simple magnetic resonance experiments, exploiting a qubit as a highly sensitive and coherent magnetic sensor, to provide clear signatures of the acceptor polarization. Moreover, we show that information could even be obtained from time-resolved electron paramagnetic resonance experiments on a randomly oriented solution of molecules. The proposed experiments will unveil the role of chiral linkers in electron transfer and could also be exploited for quantum computing applications.
We present a static and picosecond X-ray absorption study at the Cu K-edge of bis(2,9-dimethyl-1,10-phenanthroline)copper(I) (Cu(dmp)2+; dmp = 2,9-dimethyl-1,10-phenanthroline) dissolved in ...acetonitrile and dichloromethane. The steady-state photoluminescence spectra in dichloromethane and acetonitrile are also presented and show a shift to longer wavelengths for the latter, which points to a stronger stabilization of the excited complex. The fine structure features of the static and transient X-ray spectra allow an unambiguous assignment of the electronic and geometric structure of the molecule in both its ground and excited 3MLCT states. Importantly, the transient spectra are remarkably similar for both solvents, and the spectral changes can be rationalized using the optimized ground- and excited-state structures of the complex. The proposed assignment of the lifetime shortening of the excited state in donor solvents (acetonitrile) to a metal-centered exciplex is not corroborated here. Molecular dynamics simulations confirm the lack of complexation; however, in both solvents the molecules come close to the metal but undergo rapid exchange with the bulk. The shortening of the lifetime of the title complex and nine additional related complexes can be rationalized by the decrease in the 3MLCT energy. Deviations from this trend may be explained by means of the effects of the dihedral angle between the ligand planes, the solvent, and the 3MLCT-1MLCT energy gap.
We present an Fe Kα resonant inelastic X-ray scattering (RIXS) and X-ray emission (XES) study of ferrous and ferric hexacyanide dissolved in water and ethylene glycol. We observe that transitions ...below the absorption edge show that the solvent has a distinct effect on the valence electronic structure. In addition, both the RIXS and XES spectra show a stabilization of the 2p levels when dissolved in water. Using molecular dynamics simulations, we propose that this effect arises from the hydrogen-bonding interactions between the complex and nearby solvent molecules. This withdraws electron density from the ligands, stabilizing the complex but also causing a slight increase in π-backbonding.
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