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Rigorous quantum calculations for atom-molecule chemical reactions in electric fields: From single to multiple
Timur V Tscherbul1, Roman V Krems2
1Department of Physics, University of Nevada, Reno, Nevada 89557, USA.
The Journal of Chemical Physics
|November 10, 2025
Summary
We developed an efficient quantum calculation method for atom-molecule reactions in electric fields. Calculations show electric fields affect LiF + H reactions but not F + HD reactions, highlighting basis set convergence importance.
Area of Science:
- Quantum chemistry
- Chemical physics
- Computational chemistry
Background:
- Atom-molecule reactive scattering is crucial for understanding chemical reactions.
- External electric fields can influence reaction dynamics.
- Previous methods faced computational challenges in handling electric field effects.
Purpose of the Study:
- To develop an efficient quantum mechanical method for calculating atom-molecule reactive scattering cross sections in DC electric fields.
- To investigate the influence of electric fields on specific chemical reactions, namely LiF + H and F + HD.
- To address computational challenges in previous approaches by implementing an efficient asymptotic frame transformation.
Main Methods:
- Wavefunction expansion using Fock-Delves hyperspherical basis functions.
- Incorporation of electric field interactions in the total angular momentum representation.
- Efficient asymptotic frame transformation between hyperspherical and Jacobi coordinates.
Main Results:
- Calculated cross sections for LiF + H and F + HD reactions as functions of collision energy and electric field strength.
- Observed resonance structure in LiF + H reaction cross sections due to tunneling-driven interactions.
- Found no significant electric field effects on F + HD reaction at 1 K, even at high field strengths (200 kV/cm).
Conclusions:
- Basis set convergence is essential for accurately interpreting external field effects on chemical reaction dynamics.
- Reduced-basis calculations can overestimate electric field effects, which vanish with increased total angular momentum basis states.
- The developed method provides an efficient pathway for rigorous quantum calculations of field-influenced reactive scattering.
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