Two-Dimensional Electronic Spectroscopy in the Condensed Phase Using Equivariant Transformer Accelerated Molecular Dynamics Simulations
Two-dimensional electronic spectroscopy (2DES) provides rich information about how the electronic states of molecules, proteins, and solid-state materials interact with each other and their surrounding environment. Atomistic molecular dynamics simulations offer an appealing route to uncover how nuclear motions mediate electronic energy relaxation and their manifestation in electronic spectroscopies but are computationally expensive. Here we show that by using an equivariant transformer-based machine learning architecture trained with only 2500 ground state and 100 excited state electronic structure calculations, one can construct accurate machine-learned potential energy surfaces for both the ground-state electronic surface and excited-state energy gap. We demonstrate the utility of this approach for simulating the dynamics of Nile blue in ethanol, where we experimentally validate and decompose the simulated 2DES to establish the nuclear motions of the chromophore and the solvent that couple to the excited state, connecting the spectroscopic signals to their molecular origin.
Authors
- Christine M. Isborn (ORCID: https://orcid.org/0000-0002-4905-9113)
- Gabriela S. Schlau‐Cohen (ORCID: https://orcid.org/0000-0001-7746-2981)
- Michael S. Chen (ORCID: https://orcid.org/0000-0003-0767-4238)
- Tim Joachim Zuehlsdorff (ORCID: https://orcid.org/0000-0002-6960-756X)
- Andrés Montoya−Castillo (ORCID: https://orcid.org/0000-0003-3037-3695)
- Thomas E. Markland (ORCID: https://orcid.org/0000-0002-2747-0518)
- Minjung Son (ORCID: https://orcid.org/0000-0002-8385-062X)
- Angela Lee (ORCID: https://orcid.org/0000-0001-5388-8400)
- Andrew Snider
- Prachi Gupta
- Frank Hu (ORCID: https://orcid.org/0009-0001-4783-0947)
- Joseph Kelly (ORCID: https://orcid.org/0000-0001-5336-4199)
- A. Damiani
Institutions
- Boston University (US)
- Oregon State University (US)
- University of California, Merced (US)
- University of Colorado Boulder (US)
- University of Colorado System (US)
- New York University (US)
- Massachusetts Institute of Technology (US)
- Stanford University (US)
Publication Details
- Journal
- The Journal of Physical Chemistry Letters
- Published
- 2025-05-28
- DOI
- https://doi.org/10.1021/acs.jpclett.5c00911
- Citations
- 4
- Primary Topic
- Spectroscopy and Quantum Chemical Studies
- Type
- article
- Field-Weighted Citation Impact
- 4.99
Funders
- National Energy Research Scientific Computing Center
- Division of Chemistry
- Basic Energy Sciences