Quantum equilibration of the double-proton transfer in a model system porphine

There is a renewed interest in the derivation of statistical mechanics from the dynamics of closed quantum systems. A central part of this program is to understand how closed quantum systems, i.e., in the absence of a thermal bath, initialized far-from-equilibrium can share a dynamics that is typical to the relaxation towards thermal equilibrium. Equilibration dynamics has been traditionally studied with a focus on the so-called quenches of large-scale many-body systems. We consider here the equilibration of a two-dimensional molecular model system describing the double proton transfer reaction in porphine. Using numerical simulations, we show that equilibration indeed takes place very rapidly (∼200 fs) for initial states induced by pump–dump laser pulse control with energies well above the synchronous barrier. The resulting equilibration state is characterized by a strong delocalization of the probability density of the protons that can be explained, mechanistically, as the result of (i) an initial state consisting of a large superposition of vibrational states, and (ii) the presence of a very effective dephasing mechanism

Conditional Born-Oppenheimer dynamics: quantum dynamics simulations for the model porphine

We report a new theoretical approach to solve adiabatic quantum molecular dynamics halfway between wave function and trajectory-based methods. The evolution of a N- body nuclear wave function moving on a 3N-dimensional Born−Oppenheimer potential-energy hyper-surface is rewritten in terms of single-nuclei wave functions evolving nonunitarily on a 3-dimensional potential-energy surface that depends parametrically on the configuration of an ensemble of generally defined trajectories. The scheme is exact and, together with the use of trajectory-based statistical techniques, can be exploited to circumvent the calculation and storage of many-body quantities (e.g., wave function and potential-energy surface) whose size scales exponentially with the number of nuclear degrees of freedom. As a proof of concept, we present numerical simulations of a 2-dimensional model porphine where switching from concerted to sequential double proton transfer (and back) is induced quantum mechanicall

Quantum hardware simulating four-dimensional inelastic neutron scattering

Magnetic molecules, modelled as finite-size spin systems, are test-beds for quantum phenomena and could constitute key elements in future spintronics devices, long-lasting nanoscale memories or noise-resilient quantum computing platforms. Inelastic neutron scattering is the technique of choice to probe them, characterizing molecular eigenstates on atomic scales. However, although large magnetic molecules can be controllably synthesized, 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 computers have the potential to efficiently extract dynamical correlations and the associated magnetic neutron cross-section by simulating prototypical spin systems on a quantum hardware. 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

A hybrid quantum-classical method for electron-phonon systems

nteractions between electrons and phonons play a crucial role in quantum materials. Yet, there is no universal method that would simultaneously accurately account for strong electron-phonon interactions and electronic correlations. By combining methods of the variational quantum eigensolver and the variational non-Gaussian solver, we develop a hybrid quantum-classical algorithm suitable for this type of correlated systems. This hybrid method tackles systems with arbitrarily strong electron-phonon coupling without increasing the number of required qubits and quantum gates, as compared to purely electronic models. We benchmark our method by applying it to the paradigmatic Hubbard-Holstein model at half filling, and show that it correctly captures the competition between charge density wave and antiferromagnetic phases, quantitatively consistent with exact diagonalization

Library of dispersion-corrected atom-centered potentials for generalized gradient approximation functionals: Elements H, C, N, O, He, Ne, Ar, and Kr

Parameters for analytical dispersion-corrected atom-centered potentials (DCACPs) are presented to improve the description of London dispersion forces within the generalized gradient approximation functionals BLYP, BP, and PBE. A library of DCACPs for hydrogen, carbon, nitrogen, oxygen, helium, neon, argon, and krypton was obtained by calibrating against high-level CCSD(T) or configuration interaction references. The performance and transferability of DCACPs were tested on weakly bound complexes and provide excellent results throughout all investigated systems

A Quantum Dynamics Study of the Ultrafast Relaxation in a Prototypical Cu(I)-Phenanthroline

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 (S-3) is investigated using quantum nuclear dynamics. In agreement with recent experimental conclusions, we find that the system undergoes rapid (similar to 100 fs) internal conversion from S-3 into the S-2 and S-1 states at or near the FranckCondon (FC) geometry. This is preceded by a dynamic component with a time constant of similar to 400 fs, which corresponds to the flattening of the ligands associated with the pseudo JahnTeller 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 JahnTeller 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

Probing the electronic and geometric structure of ferric and ferrous myoglobins in physiological solutions by Fe K-edge absorption spectroscopy.

We present an iron K-edge X-ray absorption study of carboxymyoglobin (MbCO), nitrosylmyoglobin (MbNO), oxymyoglobin (MbO2), cyanomyoglobin (MbCN), aquomet myoglobin (metMb) and unligated myoglobin (deoxyMb) in physiological media. The analysis of the XANES region is performed using the full-multiple scattering formalism, implemented within the MXAN package. This reveals trends within the heme structure, absent from previous crystallographic and X-ray absorption analysis. In particular, the iron–nitrogen bond lengths in the porphyrin ring converge to a common value of about 2 Å, except for deoxyMb whose bigger value is due to the doming of the heme. The trends of the Fe–Nε (His93) bond length is found to be consistent with the effect of ligand binding to the iron, with the exception of MbNO, which is explained in terms of the repulsive trans effect. We derive a high resolution description of the relative geometry of the ligands with respect to the heme and quantify the magnitude of the heme doming in the deoxyMb form. Finally, time-dependent density functional theory is used to simulate the pre-edge spectra and is found to be in good agreement with the experiment. The XAS spectra typically exhibit one pre-edge feature which arises from transitions into the unoccupied dσ and dπ − πligand* orbitals. 1s → dπ transitions contribute weakly for MbO2, metMb and deoxyMb. However, despite this strong Fe d contribution these transitions are found to be dominated by the dipole (1s → 4p) moment due to the low symmetry of the heme environment

Quantum equilibration of the double-proton transfer in a model system Porphine

There is a renewed interest in the derivation of statistical mechanics from the dynamics of closed quantum systems. A central part of this program is to understand how closed quantum systems, i.e., in the absence of a thermal bath, initialized far-from-equilibrium can share a dynamics that is typical to the relaxation towards thermal equilibrium. Equilibration dynamics has been traditionally studied with a focus on the so-called quenches of large-scale many-body systems. We consider here the equilibration of a two-dimensional molecular model system describing the double proton transfer reaction in porphine. Using numerical simulations, we show that equilibration indeed takes place very rapidly (about 200 fs) for initial states induced by pump-dump laser pulse control with energies well above the synchronous barrier. The resulting equilibration state is characterized by a strong delocalization of the probability density of the protons that can be explained, mechanistically, as the result of (i) an initial state consisting of a large superposition of vibrational states, and (ii) the presence of a very effective dephasing mechanism