Electronic Coherences Built by Ultrashort Pulse Drive the Vibronic Forces at Nonadiabatic Seams

Electronic coherence; Gradient terms; Non adiabatic interactions; Non-adiabatic; Potential gradients; Pulse drive; Quantum force; Total force; Ultrashort-pulse; Vibronics; Biophysics; Atomic and Molecular Physics, and Optics; Physics and Astronomy (miscellaneous); Physical and Theoretical Chemistry

Abstract :

[en] We show that the quantum force that the electrons in a molecule exert on the nuclei remains local even in the presence of strong nonadiabatic interactions. At every geometry, the total force is the sum of a potential gradient term driven by the local population and a nonclassical, nonadiabatic force driven by the local electronic coherence. On the nonadiabatic seams, the nonadiabatic force competes effectively with the potential terms. Following a sudden photoionization, we show how the nonadiabatic component of the local force drives the dynamics of the structural Jahn–Teller rearrangement of the methane cation toward the C2v geometry using 2 effective nuclear coordinates and 3 coupled electronic states for either CH+ 4 or CD+ 4. Toward the progress in reaching shorter femtosecond resolution in time-resolved x-ray and electron diffraction experiments, our work provides a quantitative understanding and pictorial visualization of the local forces that drive ultrafast molecular rearrangement and chemical reactivity with a special reference to the role of electronic coherences and nonadiabatic couplings.

Disciplines :

Chemistry

Author, co-author :

Pandey, Gaurav ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique

Cardosa-Gutierrez, Manuel ; Theoretical Physical Chemistry, UR MOLSYS, University of Liege, Liege, Belgium

Levine, Raphael D. ; Fritz Haber Center, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, Israel ; Department of Molecular and Medical Pharmacology, David Geffen School of Medicine, University of California, Los Angeles, United States ; Department of Chemistry and Biochemistry, University of California, Los Angeles, United States

Remacle, Françoise ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique

Language :

English

Title :

Electronic Coherences Built by Ultrashort Pulse Drive the Vibronic Forces at Nonadiabatic Seams

Publication date :

19 May 2026

Journal title :

Ultrafast Science

ISSN :

2097-0331

eISSN :

2765-8791

Publisher :

American Association for the Advancement of Science

Volume :

Issue :

Pages :

0167

Peer reviewed :

Peer Reviewed verified by ORBi

Additional URL :

https://spj.science.org/doi/pdf/10.34133/ultrafastscience.0167

Funders :

F.R.S.-FNRS - Fonds de la Recherche Scientifique
ULiège - Université de Liège

Funding number :

T.0247.24,; 2.5020.11; EOS 40007519

Funding text :

PDR MOLECOH, CECI (Consortium des Equipements de calcul intensif, EOS project Tethered, IPD-STEMA

Available on ORBi :

since 30 June 2026

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