Electronic Coherences Steer the Strong Isotope Effect in the Ultrafast Jahn–Teller Structural Rearrangement of Methane Cation upon Tunnel Ionization

An ultrafast structural, Jahn-Teller (JT) driven, electronic coherence mediated quantum dynamics in the CH4+ and CD4+ cations that follows a sudden ionization by an XUV attopulse, exhibits a strong isotope effect. The JT effect makes the methane cation unstable in the Td geometry of the neutral. Upon the sudden ionization the cation is produced in a coherent superposition of three electronic states that are strongly coupled. On the ground state of the cation the few femtosecond structural rearrangement leads first to a geometrically less distorted D2d minimum followed by a reorganization to a shallow C2v minimum. The dynamics is computed for an ensemble of 8000 ions randomly oriented with respect to the polarization of the XUV pulse. The ratio, about 3, of the CD4+ and CH4+ autocorrelation functions, is in agreement with experimental measurements of the high harmonic spectra. The high value of the ratio is attributed to the faster electronic coherence dynamics in CH4+.

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Geometrical Reorganization of a Methane Cation upon a Sudden Ionization: An Isotope Effect in Electronic Non Equilibrium Quantum Dynamics

10.26434/chemrxiv.13702456.v1 ◽

2021 ◽

Author(s):

Cayo Gonçalves ◽

Raphael D. Levine ◽

Francoise Remacle

Keyword(s):

Isotope Effect ◽

Ground State ◽

Quantum Dynamics ◽

High Harmonic ◽

Electronic States ◽

Structural Rearrangement ◽

Experimental Measurements ◽

Strongly Coupled ◽

Jahn Teller ◽

Electronic Coherence

An ultrafast structural, Jahn-Teller (JT) driven, electronic coherence mediated quantum dynamics in the CH4+ and CD4+ cations that follows a sudden ionization by an XUV attopulse, exhibits a strong isotope effect. The JT effect makes the methane cation unstable in the Td geometry of the neutral. Upon the sudden ionization the cation is produced in a coherent superposition of three electronic states that are strongly coupled. On the ground state of the cation the few femtosecond structural rearrangement leads first to a geometrically less distorted D2d minimum followed by a reorganization to a shallow C2v minimum. The dynamics is computed for an ensemble of 8000 ions randomly oriented with respect to the polarization of the XUV pulse. The ratio, about 3, of the CD4+ and CH4+ autocorrelation functions, is in agreement with experimental measurements of the high harmonic spectra. The high value of the ratio is attributed to the faster electronic coherence dynamics in CH4+.

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Polar Jahn-Teller centers and the anomalous isotope effect in copper-oxygen high-T c superconductors

Journal of Experimental and Theoretical Physics ◽

10.1134/1.558134 ◽

1997 ◽

Vol 84 (2) ◽

pp. 354-359 ◽

Cited By ~ 12

Author(s):

A. S. Moskvin ◽

Yu. D. Panov

Keyword(s):

Isotope Effect ◽

Jahn Teller

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Isotope effect on the static distortion and the dynamics of partially deuteriated Jahn-Teller active radical cations: cyclopropane-1,1-d2

The Journal of Physical Chemistry ◽

10.1021/j100355a015 ◽

1989 ◽

Vol 93 (18) ◽

pp. 6642-6645 ◽

Cited By ~ 12

Author(s):

K. Matsuura ◽

K. Nunome ◽

M. Okazaki ◽

K. Toriyama ◽

M. Iwasaki

Keyword(s):

Isotope Effect ◽

Radical Cations ◽

Jahn Teller ◽

Static Distortion

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Polar Jahn-Teller Centers and isotope effect in copper oxide high-Tc-superconductors

Physica C Superconductivity ◽

10.1016/s0921-4534(97)01028-9 ◽

1997 ◽

Vol 282-287 ◽

pp. 1813-1814

Author(s):

A.S. Moskvin ◽

A.S. Ovchinnikov ◽

Yu.D. Panov ◽

M.A. Sidorov

Keyword(s):

Copper Oxide ◽

Isotope Effect ◽

High Tc Superconductors ◽

High Tc ◽

Jahn Teller

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Ultrafast geometrical reorganization of a methane cation upon a sudden ionization: An isotope effect in electronic non equilibrium quantum dynamics

Physical Chemistry Chemical Physics ◽

10.1039/d1cp01029h ◽

2021 ◽

Author(s):

Cayo C. M. Goncalves ◽

Raphael D. Levine ◽

Francoise Remacle

Keyword(s):

Isotope Effect ◽

Quantum Dynamics ◽

Jahn Teller ◽

Electronic Coherence ◽

Non Equilibrium

An ultrafast structural, Jahn-Teller (JT) driven, electronic coherence mediated quantum dynamics in the CH4+ and CD4+ cations that follows a sudden ionization by an XUV attopulse, exhibits a strong isotope...

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