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

Abstract

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 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 et al. [ Science 2015 , 350 , 1338], 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.

arXiv comment16 pages, 1 figure, and two tables. Supplementary Material included. Accepted for publication in The Journal of Physical Chemistry A

References in corpus (10)

• Excited state quantum phase transitions in many-body systems
• Improved HCN/HNC linelist, model atmospheres and synthetic spectra for WZ Cas
• Quantum phase transitions in the interacting boson model
• Quantum chaos: an introduction via chains of interacting spins-1/2
• Excited-state quantum phase transitions in many-body systems with infinite-range interaction: Localization, dynamics, and bifurcation
• Dynamics in spinor condensates controlled by a microwave dressing field
• Structure of eigenstates and quench dynamics at an excited state quantum phase transition
• Lifshitz and Excited State Quantum Phase Transitions in Microwave Dirac Billiards
• Quantum quench dynamics in Dicke superradiance models
• Effects of excited state quantum phase transitions on system dynamics

Cited by in corpus (18)

• Excited-state quantum phase transitions
• Probing excited-state quantum phase transition in a quantum many body system via out-of-time-ordered correlator
• Spectral kissing and its dynamical consequences in the squeeze-driven Kerr oscillator
• Simulating Chemistry on Bosonic Quantum Devices
• Excited state quantum phase transitions in the bending spectra of molecules
• Signatures of excited state quantum phase transitions in quantum many body systems: Phase space analysis
• Excited-State Quantum Phase Transitions in the Anharmonic Lipkin-Meshkov-Glick Model I: Static Aspects
• Anharmonicity-induced excited-state quantum phase transition in the symmetric phase of the two-dimensional limit of the vibron model
• Quantum fidelity susceptibility in excited state quantum phase transitions: application to the bending spectra of nonrigid molecules
• Characterizing the excited-state quantum phase transition via the dynamical and statistical properties of the diagonal entropy
• Measurements of rate coefficients of CN${}^{+}$, HCN${}^{+}$ and HNC${}^{+}$ collisions with H${}_2$ at cryogenic temperatures
• Excited-State Quantum Phase Transitions in the Anharmonic Lipkin-Meshkov-Glick Model: Dynamical Aspects
• Complex density of continuum states in resonant quantum tunneling
• Continuum analogues of excited-state quantum phase transitions
• Unmasking the physical information inherent to interstellar spectral line profiles with Machine Learning. I. Application of LTE to HCN and HNC transitions
• Excited stated quantum phase transitions and the entropy of the work distribution in the anharmonic Lipkin-Meshkov-Glick model
• Stabilization of product states and excited-state quantum phase transitions in a coupled qubit-field system
• Phenomenological characterization of the isomerization transition state of carbonyl sulfide