Intramolecular Nuclear Flux Densities

Barth, Ingo; Daniel, Christopher G.; Gindensperger, Etienne; Manz, J.; Pérez-Torres, Jhon Fredy; Schild, Axel; Stemmle, Christian; Sulzer, David; Yang, Y. Y.

doi:10.1142/9789814619042_0002

Cited by 7 publications

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“…This reduction of complexity can be achieved if the N nuclei are considered to be classical particles with their location being described by a point in the 3 N -dimensional configuration space, which is equivalent to N points in a three-dimensional space. However, despite the success of this classical picture the nuclei are quantum particles, as is exemplified by recent interest in measuring e.g., the nuclear probability density (Shapiro, 1981; Zewail, 2000; Jurek et al, 2004; Ergler et al, 2006; Schmidt et al, 2012; Kimberg and Miron, 2014; Zeller et al, 2016) or the nuclear flux (current) density (Manz et al, 2013; Barth et al, 2015; Bredtmann et al, 2015). Hence, for the chemical picture to make sense it should be possible to obtain it quantum-mechanically without the need for (semi-)classical approximations.…”

Section: Introductionmentioning

confidence: 99%

“…the nuclear probability density [17,18,19,20,21,22,23] or the nuclear flux (current) density. [24,25,26] An intriguing example of the quantum nature of the nuclei is the measurement of the nuclear density of a vibrationally excited H + 2 -molecules by means of Coulomb explosion imaging. [21] The measured nuclear density, which depends only on the relative distance of the two nuclei, shows the expected nodal pattern of vibrationally excited states.…”

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confidence: 99%

“…25) * A factor π N/2 could be added to have Γ[N] (x) properly normalized. Instead, it is included in the definition of the polynomial coefficients.…”

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On the Probability Density of the Nuclei in a Vibrationally Excited Molecule

Schild

2019

Front. Chem.

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For localized and oriented vibrationally excited molecules, the qualitative features of the one-body probability density of the nuclei (one-nucleus density) are investigated. Like the familiar and widely used one-electron density that represents the probability of finding an electron at a given location in space, the one-nucleus density represents the probability of finding a nucleus at a given position in space independent of the location of the other nuclei and independent of their type. In contrast to the electrons, however, the nuclei are comparably localized. Due to this localization of the individual nuclei, the one-nucleus density provides a quantum-mechanical representation of the “chemical picture” of the molecule as an object that can largely be understood in a three-dimensional space, even though its full nuclear probability density is defined on the high-dimensional configuration space of all the nuclei. We study how the nodal structure of the wavefunctions of vibrationally excited states translates to the one-nucleus density. It is found that nodes do not necessarily lead to visible changes in the one-nucleus density: Already for relatively small molecules, only certain vibrational excitations change the one-nucleus density qualitatively compared to the ground state. It turns out that there are simple rules for predicting the shape of the one-nucleus density from the normal mode coordinates. A Python module for the computation of the one-nucleus density is provided at https://gitlab.com/axelschild/mQNMc

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Section: Introductionmentioning

confidence: 99%

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On the Probability Density of the Nuclei in a Vibrationally Excited Molecule

Schild

2019

Front. Chem.

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“…The results for the CENFs for this reaction without an external field stimulated the present search for corresponding phenomena in the environment of an external electric field (see also ref ). In a broader perspective, this article should add new discoveries to the quantum theory of intramolecular fluxes, including electronic fluxes, − nuclear fluxes, ,− and CENFs ,,− (see also refs − ).…”

Section: Introductionmentioning

confidence: 99%

Concerted Electronic and Nuclear Fluxes During Coherent Tunnelling in Asymmetric Double-Well Potentials

Bredtmann¹,

Manz

Zhao³

2016

J. Phys. Chem. A

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The quantum theory of concerted electronic and nuclear fluxes (CENFs) during coherent periodic tunnelling from reactants (R) to products (P) and back to R in molecules with asymmetric double-well potentials is developed. The results are deduced from the solution of the time-dependent Schrödinger equation as a coherent superposition of two eigenstates; here, these are the two states of the lowest tunnelling doublet. This allows the periodic time evolutions of the resulting electronic and nuclear probability densities (EPDs and NPDs) as well as the CENFs to be expressed in terms of simple sinusodial functions. These analytical results reveal various phenomena during coherent tunnelling in asymmetric double-well potentials, e.g., all EPDs and NPDs as well as all CENFs are synchronous. Distortion of the symmetric reference to a system with an asymmetric double-well potential breaks the spatial symmetry of the EPDs and NPDs, but, surprisingly, the symmetry of the CENFs is conserved. Exemplary application to the Cope rearrangement of semibullvalene shows that tunnelling of the ideal symmetric system can be suppressed by asymmetries induced by rather small external electric fields. The amplitude for the half tunnelling, half nontunnelling border is as low as 0.218 × 10(-8) V/cm. At the same time, the delocalized eigenstates of the symmetric reference, which can be regarded as Schrödinger's cat-type states representing R and P with equal probabilities, get localized at one or the other minima of the asymmetric double-well potential, representing either R or P.

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“…Polycyclic aromatic hydrocarbons (PAHs), which are two-dimensional (2D), are typical organic materials. Attention has recently been paid to PAHs as organic molecular electronic materials, particularly for field-effect transistor devices. − In addition, from the viewpoint of the ultrafast coherent electromagnetic response of π electrons in aromatic ring molecules, − it is important to explore the possibility of such an optical response in PAHs. Control of electrons in atoms and molecules has been possible because of rapid advances in laser science and technology as well as quantum dynamical theory of electrons in molecules. − The control of π-electrons in PAHs by lasers is one of the attractive research targets to create ring currents and current-induced magnetic fields.…”

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confidence: 99%

Quantum Design of π-Electron Ring Currents in Polycyclic Aromatic Hydrocarbons: Parallel and Antiparallel Ring Currents in Naphthalene

Mineo

Fujimura

2017

J. Phys. Chem. Lett.

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Control of π-electrons in polycyclic aromatic hydrocarbons (PAHs) is one of the fundamental issues in optoelectronics for ultrafast optical switching devices. We have proposed an effective scenario for design of the generation of coherent ring currents in naphthalene (D), which is the smallest unit of planar PAHs. It has been demonstrated by using quantum chemical calculations and quantum optimal control (QOC) simulations that two types of ring currents, parallel and antiparallel, can be generated by resonance excitations by two linearly polarized lasers. A parallel (antiparallel) ring current means that the currents of two benzene rings run in the same (opposite) directions. The two types of ring currents may be experimentally identified by magnetic force microscopy. The QOC simulations indicate that a parallel ring current can be generated by using continuous wave and Gaussian pulse lasers with their time delay without relying on a sophisticated experimental apparatus. The present results provide a guiding principle of coherent π-electronics in PAHs for next-generation organic optical switching devices.

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Intramolecular Nuclear Flux Densities

Cited by 7 publications

References 0 publications

On the Probability Density of the Nuclei in a Vibrationally Excited Molecule

On the Probability Density of the Nuclei in a Vibrationally Excited Molecule

Concerted Electronic and Nuclear Fluxes During Coherent Tunnelling in Asymmetric Double-Well Potentials

Quantum Design of π-Electron Ring Currents in Polycyclic Aromatic Hydrocarbons: Parallel and Antiparallel Ring Currents in Naphthalene

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