Heavy-quark mesons in the diabatic approach: string breaking and the quarkoniumlike spectrum

The Born-Oppenheimer approximation provides a description of heavy-quark mesons firmly based on lattice QCD, but its validity is limited to the lightest states lying far below the first open-flavour meson-meson threshold. This limitation can be overcome in the diabatic framework, a formalism first introduced in molecular physics, where the dynamics is encoded in a potential matrix whose elements can be derived from unquenched lattice QCD studies of string breaking. The off-diagonal elements of the potential matrix provide interaction between heavy quark-antiquark and meson-meson pairs, from which the mixing of quarkonium states with molecular components and the OZI-allowed strong decay widths are directly calculated. This allows for a QCD-based unified description of conventional quarkonium and unconventional mesons containing quark-antiquark and meson-meson components, what has proved to be successful for charmoniumlike and bottomoniumlike resonances.

Lattice dynamics in CePd2Al2 and LaPd2Al2

The interaction between phonons and 4f electrons, which is forming a new quantum state (quasi-bound state) beyond Born-Oppenheimer approximation, is very prominent and lattice dynamics plays here a key role. There is only a small number of compounds in which the experimental observation suggest such a scenario. One of these compounds is CePd2Al2. Here the study of phonon dispersion curves of (Ce,La)Pd2Al2 at 1.5, 7.5, 80 and 300 K is presented. The inelastic X-ray scattering technique was used for mapping the phonon modes at X and Z points as well as in Λ and Δ directions, where the symmetry analysis of phonon modes was performed. The measured spectra are compared with the theoretical calculation, showing very good agreement. The measurements were performed in several Brillouin zones allowing the reconstruction of phonon dispersion curves. The results are discussed with respect to the magneto-elastic interaction and are compared with other cerium compounds. The phonon mode symmetry A1g was found to be unaffected by the interaction, which is in contrast to previous assumptions.

Full-dimensional quantum stereodynamics of the non-adiabatic quenching of OH(A2Σ+) by H2

The Born–Oppenheimer approximation, assuming separable nuclear and electronic motion, is widely adopted for characterizing chemical reactions in a single electronic state. However, the breakdown of the Born–Oppenheimer approximation is omnipresent in chemistry, and a detailed understanding of the non-adiabatic dynamics is still incomplete. Here we investigate the non-adiabatic quenching of electronically excited OH(A2Σ+) molecules by H2 molecules using full-dimensional quantum dynamics calculations for zero total nuclear angular momentum using a high-quality diabatic-potential-energy matrix. Good agreement with experimental observations is found for the OH(X2Π) ro-vibrational distribution, and the non-adiabatic dynamics are shown to be controlled by stereodynamics, namely the relative orientation of the two reactants. The uncovering of a major (in)elastic channel, neglected in a previous analysis but confirmed by a recent experiment, resolves a long-standing experiment–theory disagreement concerning the branching ratio of the two electronic quenching channels.

An Investigation into the Approximations Used in Wave Packet Molecular Dynamics for the Study of Warm Dense Matter

Wave packet molecular dynamics (WPMD) has recently received a lot of attention as a computationally fast tool with which to study dynamical processes in warm dense matter beyond the Born–Oppenheimer approximation. These techniques, typically, employ many approximations to achieve computational efficiency while implementing semi-empirical scaling parameters to retain accuracy. We investigated three of the main approximations ubiquitous to WPMD: a restricted basis set, approximations to exchange, and the lack of correlation. We examined each of these approximations in regard to atomic and molecular hydrogen in addition to a dense hydrogen plasma. We found that the biggest improvement to WPMD comes from combining a two-Gaussian basis with a semi-empirical correction based on the valence-bond wave function. A single parameter scales this correction to match experimental pressures of dense hydrogen. Ultimately, we found that semi-empirical scaling parameters are necessary to correct for the main approximations in WPMD. However, reducing the scaling parameters for more ab-initio terms gives more accurate results and displays the underlying physics more readily.

Stereodynamical Control of Nonadiabatic Quenching Dynamics of OH(A2S+) by H2: Full-Dimensional Quantum Dynamics

The breakdown of the Born-Oppenheimer approximation is omnipresent in chemistry, but our detailed understanding of the nonadiabatic dynamics is still incomplete. In the present work, nonadiabatic quenching of electronically excited OH(A2S+) molecules by H2 molecules is investigated by a full-dimensional quantum dynamical method using a high quality diabatic potential energy matrix. Good agreement with experiment is found for the OH(X2P) ro-vibrational and L-doublet distributions. Furthermore, the nonadiabatic dynamics is shown to be controlled by stereodynamics, namely the orientation of the two reactants. The uncovering of a major (in)elastic channel, neglected in all previous analyses, resolves a long-standing experiment-theory disagreement concerning the branching ratio of the two electronic quenching channels.

High-Fidelity First Principles Nonadiabaticity: Diabatization, Analytic Representation of Global Diabatic Potential Energy Matrices, and Quantum Dynamics

Nonadiabatic dynamics, which goes beyond the Born-Oppenheimer approximation, has increasingly been shown to play an important role in chemical processes, particularly those involving electronically excited states. Understanding multistate dynamics requires...

Ридберговские состояния радикала ОН

We study Rydberg states of radical in adiabatic (rotational Born–Oppenheimer) approximation as well as in the inverse limit. The needed value, d = 0.833, of the OH+cation’s dipole moment was calculated using the RCCSD(T)/aug-cc-pV5Zmethod. Our calculations show that a dipole moment of this magnitude influence weakly on the energies of the Rydberg states. The exception are the states originating from s-states in the central-symmetric field, which are influenced significantly by the cation dipole moment. In the inverse Born–Oppenheimer limit, we study in detail the dependence of the Rydberg spectrum upon the total angular momentum, J, of the molecule. This dependence substantially differs from the well-known dependence, ∼J(J + 1), of the rotating top energy on its total momentum.

Analog quantum simulation of chemical dynamics

Ultrafast chemical reactions are difficult to simulate because they involve entangled, many-body wavefunctions whose computational complexity grows rapidly with molecular size. In photochemistry, the breakdown of the Born-Oppenheimer approximation further...