Collision-Assisted Spectroscopy of HCN above the Isomerization Barrier

Lessen, D.; Baskin, J. Spencer; Jones, Christopher M.; Tian, He; Carrasquillo-Molina, Edwin

doi:10.1021/jp021075n

Cited by 3 publications

(1 citation statement)

References 32 publications

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“…On the other hand, the molecule HCN is one of the best‐known molecules, from the point of view of infrared spectroscopy. Probably, there are the most states assigned, at all, see Mellau et al48 and references therein, and ref 65…”

Section: Discussionmentioning

confidence: 99%

Transition state theory with Tsallis statistics

Quapp

Zech

2009

J Comput Chem

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We discuss the rate of an elementary chemical reaction. We use the reaction path and especially its saddle point on the potential energy surface. The reaction path connects reactant and product of a reaction over the transition state (TS). Usually, the TS is assumed near or at the single saddle point of the reaction path. By means of comparison of the statistics of states at the reactant and at the TS, one can estimate the reaction rate by the Eyring theory. We propose to use the Tsallis statistics at the TS, a statistics of seldom accidents. Thus, we propose to generalize the well-known Boltzmann-Gibbs statistics, which is the limiting case of the Tsallis statistics. We use features of this nonextensive thermostatistics. The basic properties of the statistics are used to derive (approximated) partition functions, and they are applied on reaction rates. The approximation includes a factorization of the partition functions. The theory is applied to HCN isomerization to HNC, and to the reaction H(2) + CN --> H + HCN. It allows an accordance with experimental estimations of the reaction rates.

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Section: Discussionmentioning

confidence: 99%

Transition state theory with Tsallis statistics

Quapp

Zech

2009

J Comput Chem

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Attophotochemistry: Coherent Electronic Dynamics and Nuclear Motion

Ajay

Komarova

Wildenberg

et al. 2018

Attosecond Molecular Dynamics

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We describe and discuss the theoretical methodology we use to analyze and predict novel chemical phenomena made possible by attosecond electronic excitation. We describe the dynamics by solving the time dependent Schrödinger equation with the laser pulse treated exactly as part of the Hamiltonian. We include the explicit onset of the nuclear motion following such an ultrafast excitation. The coupling to the nuclei is discussed when using either an adiabatic or a diabatic basis for the electronic dynamics. We begin by analyzing the chemical physics that can be realized by such an ultrafast excitation. Driving chemical reactions specifically towards new channels by selective attosecond excitation is explored as well as the physical parameters that can be used in such a control. Elucidating the role of other variables such as the mass is also discussed. The results are illustrated by recent applications primarily to the N2, LiH and HCN systems.

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Pumping and probing vibrational modulated coupled electronic coherence in HCN using short UV fs laser pulses: a 2D quantum nuclear dynamical study

Wildenberg

Mignolet

Levine

et al. 2017

Phys. Chem. Chem. Phys.

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The coupled electronic-nuclear coherent dynamics induced by a short strong VUV fs pulse in the low excited electronic states of HCN is probed by transient absorption spectroscopy with a second weaker fs UV pulse. The nuclear time-dependent Schrodinger equation is solved on a 2D nuclear grid with several electronic states with a Hamiltonian including the dipole coupling to the pump and the probe electric fields. The two internal nuclear coordinates describe the motion of the light H atom. There is a band of several excited electronic states at about 8 eV above the ground state (GS) that is transiently accessed by the pump pulse. We tailored the pump so as to selectively populate the lowest 1A'' electronic state thereby the pulse creates an electronic coherence with the GS. Our simulations show that this electronic coherence is modulated by the nuclear motion and persists all the way to dissociation on the 1A'' state. Transient absorption spectra computed as a function of the delay time between the pump and the probe pulses provide a detailed probe of the electronic amplitude and its phase, as well as of the modulation of the electronic coherence by the nuclear motion, both bound and dissociative.

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Collision-Assisted Spectroscopy of HCN above the Isomerization Barrier

Cited by 3 publications

References 32 publications

Transition state theory with Tsallis statistics

Transition state theory with Tsallis statistics

Attophotochemistry: Coherent Electronic Dynamics and Nuclear Motion

Pumping and probing vibrational modulated coupled electronic coherence in HCN using short UV fs laser pulses: a 2D quantum nuclear dynamical study

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