QM/MM Modeling of Vibrational Polariton Induced Energy Transfer and Chemical Dynamics

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11 Scopus citations


Vibrational strong coupling (VSC) provides a novel means to modify chemical reactions and energy transfer pathways. To efficiently model chemical dynamics under VSC in the collective regime, herein a hybrid quantum mechanical/molecular mechanical (QM/MM) cavity molecular dynamics (CavMD) scheme is developed and applied to an experimentally studied chemical system. This approach can achieve linear scaling with respect to the number of molecules for a dilute solution under VSC by assuming that each QM solute molecule is surrounded by an independent MM solvent bath. Application of this approach to a dilute solution of Fe(CO)5 in n-dodecane under VSC demonstrates polariton dephasing to the dark modes and polariton-enhanced molecular nonlinear absorption. These simulations predict that strongly exciting the lower polariton may provide an energy transfer pathway that selectively excites the equatorial CO vibrations rather than the axial CO vibrations. Moreover, these simulations also directly probe the cavity effect on the dynamics of the Fe(CO)5 Berry pseudorotation reaction for comparison to recent two-dimensional infrared spectroscopy experiments. This theoretical approach is applicable to a wide range of other polaritonic systems and provides a tool for exploring the use of VSC for selective infrared photochemistry.

Original languageEnglish (US)
Pages (from-to)377-384
Number of pages8
JournalJournal of the American Chemical Society
Issue number1
StatePublished - Jan 11 2023
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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