Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userCalculation of Transition State Energies in the HCN-HNC Isomerization with an Algebraic Model
68
0
0.0
(
0
)
Added by
Francisco P\\'erez-Bernal
Publication date
2019
fields
Physics
and research's language is
English
Ask ChatGPT about the research
No Arabic 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 systems 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.
rate research
Read More
In a previous article [J. Chem. Phys. 138, 084108 (2013)], we showed that the $tto 0_+$ limit of ring-polymer molecular dynamics (RPMD) rate-theory is also the $tto 0_+$ limit of a new type of quantum flux-side time-correlation function, in which the dividing surfaces are invariant to imaginary-time translation; in other words, that RPMD transition-state theory (RPMD-TST) is a $tto 0_+$ quantum transition-state theory (QTST). Recently, Jang and Voth [J. Chem. Phys. 144, 084110 (2016)] rederived this quantum $tto 0_+$ limit, and claimed that it gives instead the centroid-density approximation. Here we show that the $tto 0_+$ limit derived by Jang and Voth is in fact RPMD-TST.
A reduced two dimensional model is used to study Ketene isomerization reaction. In light of recent results by Ulusoy textit{et al.} [J. Phys. Chem. A {bf 117}, 7553 (2013)], the present work focuses on the generalization of the roaming mechanism to the Ketene isomerization reaction by applying our phase space approach previously used to elucidate the roaming phenomenon in ion-molecule reactions. Roaming is again found be associated with the trapping of trajectories in a phase space region between two dividing surfaces; trajectories are classified as reactive or nonreactive, and are further naturally classified as direct or non-direct (roaming). The latter long-lived trajectories are trapped in the region of non-linear mechanical resonances, which in turn define alternative reaction pathways in phase space. It is demonstrated that resonances associated with periodic orbits provide a dynamical explanation of the quantum mechanical resonances found in the isomerization rate constant calculations by Gezelter and Miller [J. Chem. Phys. {bf 103}, 7868-7876 (1995)]. Evidence of the trapping of trajectories by `sticky resonant periodic orbits is provided by plotting Poincare surfaces of section, and a gap time analysis is carried out in order to investigate the statistical assumption inherent in transition state theory for Ketene isomerization.
HNC and HCN, typically used as dense gas tracers in molecular clouds, are a pair of isomers that have great potential as a temperature probe because of temperature dependent, isomer-specific formation and destruction pathways. Previous observations of the HNC/HCN abundance ratio show that the ratio decreases with increasing temperature, something that standard astrochemical models cannot reproduce. We have undertaken a detailed parameter study on which environmental characteristics and chemical reactions affect the HNC/HCN ratio and can thus contribute to the observed dependence. Using existing gas and gas-grain models updated with new reactions and reaction barriers, we find that in static models the H + HNC gas-phase reaction regulates the HNC/HCN ratio under all conditions, except for very early times. We quantitively constrain the combinations of H abundance and H + HNC reaction barrier that can explain the observed HNC/HCN temperature dependence and discuss the implications in light of new quantum chemical calculations. In warm-up models, gas-grain chemistry contributes significantly to the predicted HNC/HCN ratio and understanding the dynamics of star formation is therefore key to model the HNC/HCN system.
Bright HNC 1--0 emission has been found towards several Seyfert galaxies. This is unexpected since traditionally HNC is a tracer of cold (10 K) gas, and the molecular gas of luminous galaxies like Seyferts is thought to have bulk kinetic temperatures surpassing 50 K. In this work we aim to distinguish the cause of the bright HNC and to model the physical conditions of the HNC and HCN emitting gas. We have used SEST, JCMT and IRAM 30m telescopes to observe HNC 3-2 and HCN 3-2 line emission in a selection of 5 HNC-luminous Seyfert galaxies. We estimate and discuss the excitation conditions of HCN and HNC in NGC 1068, NGC 3079, NGC 2623 and NGC 7469, based on the observed 3-2/1-0 line intensity ratios. We also observed CN 1-0 and 2-1 emission and discuss its role in photon and X-ray dominated regions. HNC 3-2 was detected in 3 galaxies (NGC 3079, NGC 1068 and NGC 2623). HCN 3-2 was detected in NGC 3079, NGC 1068 and NGC 1365. The HCN 3-2/1-0 ratio is lower than 0.3 only in NGC 3079, whereas the HNC 3-2/1-0 ratio is larger than 0.3 only in NGC 2623. The HCN/HNC 1-0 and 3-2 line ratios are larger than unity in all the galaxies. The HCN/HNC 3-2 line ratio is lower than unity only in NGC 2623, similar to Arp 220, Mrk 231 and NGC 4418. In three of the galaxies the HNC emissions emerge from gas of densities n<10^5 cm^3, where the chemistry is dominated by ion-neutral reactions. In NGC 1068 the emission of HNC emerges from lower (<10^5 cm^3) density gas than HCN (>10^5 cm^3). Instead, the emissions of HNC and HCN emerge from the same gas in NGC 3079. The observed HCN/HNC and CN/HCN line ratios favor a PDR scenario, rather than an XDR one. However, the N(HNC)/N(HCN) column density ratios obtained for NGC 3079 can be found only in XDR environments.
Structural transformations in molecules and solids have generally been studied in isolation, while intermediate systems have eluded characterization. We show that a pair of CdS cluster isomers provides an advantageous experimental platform to study isomerization in well-defined atomically precise systems. The clusters coherently interconvert over an est. 1 eV energy barrier with a 140 meV shift in their excitonic energy gaps. There is a diffusionless, displacive reconfiguration of the inorganic core (solid-solid transformation) with first order (isomerization-like) transformation kinetics. Driven by a distortion of the ligand binding motifs, the presence of hydroxyl species changes the surface energy via physisorption, which determines phase stability in this system. This reaction possesses essential characteristics of both solid-solid transformations and molecular isomerizations, and bridges these disparate length scales.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
