Simulating Attochemistry: Which Dynamics Method to Use?

• Published in: The journal of physical chemistry letters Vol. 15; no. 13; pp. 3646 - 3652
• Main Authors: Tran, Thierry, Ferté, Anthony, Vacher, Morgane
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 04.04.2024
• Subjects: Chemical Sciences; Physical Insights into Light Interacting with Matter
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.4c00106

Attochemistry aims to exploit the properties of coherent electronic wavepackets excited via attosecond pulses to control the formation of photoproducts. Such molecular processes can, in principle, be simulated with various nonadiabatic dynamics methods, yet the impact of the approximations underlying the methods is rarely assessed. The performances of widely used mixed quantum-classical approaches, Tully surface hopping, and classical Ehrenfest methods are evaluated against the high-accuracy DD-vMCG quantum dynamics. This comparison is conducted for the valence ionization of fluorobenzene. Analyzing the nuclear motion induced in the branching space of the nearby conical intersection, the results show that the mixed quantum-classical methods reproduce quantitatively the average motion of a quantum wavepacket when initiated on a single electronic state. However, they fail to properly capture the nuclear motion induced by an electronic wavepacket along the derivative coupling, the latter originating from the quantum electronic coherence property, key to attochemistry.