Calculation of Transition State Energies in the HCN-HNC Isomerization with an Algebraic Model.

Recent works have shown that the spectroscopic access to highly excited states provides enough information to characterize transition states in isomerization reactions. Here, we show that information about the transition state of the bond-breaking HCN-HNC isomerization reaction can also be achieved with the two-dimensional limit of the algebraic vibron model. We describe the system's bending vibration with the algebraic Hamiltonian and use its classical limit to characterize the transition state. Using either the coherent state formalism or a recently proposed approach by Baraban [ Science 2015 , 350 , 1338 - 1342 ], we obtain an accurate description of the isomerization transition state. In addition, we show that the energy-level dynamics and the transition state wave function structure indicate that the spectrum in the vicinity of the isomerization saddle point can be understood in terms of the formalism for excited-state quantum phase transitions.

A study of the bending motion in tetratomic molecules by the algebraic operator expansion method.

We study the bending motion in the tetratomic molecules C2H2 (X̃ (1)Σg (+)), C2H2 (à (1)Au) trans-S1, C2H2 (à (1)A2) cis-S1, and X̃ (1)A1 H2CO. We show that the algebraic operator expansion method with only linear terms comprised of the basic operators is able to describe the main features of the level energies in these molecules in terms of two (linear) or three (trans-bent, cis-bent, and branched) parameters. By including quadratic terms, the rms deviation in comparison with experiment goes down to typically ∼10 cm(-1) over the entire range of energy 0-6000 cm(-1). We determine the parameters by fitting the available data, and from these parameters we construct the algebraic potential functions. Our results are of particular interest in high-energy regions where spectra are very congested and conventional methods, force-field expansions or Dunham-expansions plus perturbations, are difficult to apply.

Simulating Chemistry on Bosonic Quantum Devices.

Bosonic quantum devices offer a novel approach to realize quantum computations, where the quantum two-level system (qubit) is replaced with the quantum (an)harmonic oscillator (qumode) as the fundamental building block of the quantum simulator. The simulation of chemical structure and dynamics can then be achieved by representing or mapping the system Hamiltonians in terms of bosonic operators. In this Perspective, we review recent progress and future potential of using bosonic quantum devices for addressing a wide range of challenging chemical problems, including the calculation of molecular vibronic spectra, the simulation of gas-phase and solution-phase adiabatic and nonadiabatic chemical dynamics, the efficient solution of molecular graph theory problems, and the calculations of electronic structure.

Spectral kissing and its dynamical consequences in the squeeze-driven Kerr oscillator.

Transmon qubits are the predominant element in circuit-based quantum information processing, such as existing quantum computers, due to their controllability and ease of engineering implementation. But more than qubits, transmons are multilevel nonlinear oscillators that can be used to investigate fundamental physics questions. Here, they are explored as simulators of excited state quantum phase transitions (ESQPTs), which are generalizations of quantum phase transitions to excited states. We show that the spectral kissing (coalescence of pairs of energy levels) experimentally observed in the effective Hamiltonian of a driven SNAIL-transmon is an ESQPT precursor. We explore the dynamical consequences of the ESQPT, which include the exponential growth of out-of-time-ordered correlators, followed by periodic revivals, and the slow evolution of the survival probability due to localization. These signatures of ESQPT are within reach for current superconducting circuits platforms and are of interest to experiments with cold atoms and ion traps.

Signatures of excited-state quantum phase transitions in quantum many-body systems: Phase space analysis.

Using the Husimi quasiprobability distribution, we investigate the phase space signatures of excited-state quantum phase transitions (ESQPTs) in the Lipkin-Meshkov-Glick and coupled top models. We show that the ESQPT is evinced by the dynamics of the Husimi function, that exhibits a distinct time dependence in the different ESQPT phases. We also discuss how to identify the ESQPT signatures from the long-time averaged Husimi function and its associated marginal distributions. Moreover, from the calculated second moment and Wherl entropy of the long-time averaged Husimi function, we estimate the critical points of the ESQPT in both models, obtaining a good agreement with analytical (mean field) results. We provide a firm evidence that phase space methods are both a new probe for the detection and a valuable tool for the study of ESQPTs.

Characterizing the Lipkin-Meshkov-Glick model excited-state quantum phase transition using dynamical and statistical properties of the diagonal entropy.

Using the diagonal entropy, we analyze the dynamical signatures of the Lipkin-Meshkov-Glick model excited-state quantum phase transition (ESQPT). We first show that the time evolution of the diagonal entropy behaves as an efficient indicator of the presence of an ESQPT. We also compute the probability distribution of the diagonal entropy values over a certain time interval and we find that the resulting distribution provides a clear distinction between the different phases of ESQPT. Moreover, we observe that the probability distribution of the diagonal entropy at the ESQPT critical point has a universal form, well described by a beta distribution, and that a reliable detection of the ESQPT can be obtained from the diagonal entropy central moments.

Identifying the order of a quantum phase transition by means of Wehrl entropy in phase space.

We propose a method to identify the order of a quantum phase transition by using area measures of the ground state in phase space. We illustrate our proposal by analyzing the well known example of the quantum cusp and four different paradigmatic boson models: Dicke, Lipkin-Meshkov-Glick, interacting boson model, and vibron model.