Cavity Casimir-Polder Forces and Their Effects in Ground-State Chemical Reactivity
Here, we present a fundamental study on how the ground-state chemical reactivity of a single molecule can be modified in a QED scenario, i.e., when it is placed inside a nanoscale cavity and there is strong coupling between the cavity field and vibrational modes within the molecule. We work with a m...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
American Physical Society
2019-06-01
|
| Series: | Physical Review X |
| Online Access: | http://doi.org/10.1103/PhysRevX.9.021057 |
| _version_ | 1819009094100451328 |
|---|---|
| author | Javier Galego Clàudia Climent Francisco J. Garcia-Vidal Johannes Feist |
| author_facet | Javier Galego Clàudia Climent Francisco J. Garcia-Vidal Johannes Feist |
| author_sort | Javier Galego |
| collection | DOAJ |
| description | Here, we present a fundamental study on how the ground-state chemical reactivity of a single molecule can be modified in a QED scenario, i.e., when it is placed inside a nanoscale cavity and there is strong coupling between the cavity field and vibrational modes within the molecule. We work with a model system for the molecule (Shin-Metiu model) in which nuclear, electronic, and photonic degrees of freedom are treated on the same footing. This simplified model allows the comparison of exact quantum reaction rate calculations with predictions emerging from transition state theory based on the cavity Born-Oppenheimer approach. We demonstrate that QED effects are indeed able to significantly modify activation barriers in chemical reactions and, as a consequence, reaction rates. The critical physical parameter controlling this effect is the permanent dipole of the molecule and how this magnitude changes along the reaction coordinate. We show that the effective coupling can lead to significant single-molecule energy shifts in an experimentally available nanoparticle-on-mirror cavity. We then apply the validated theory to a realistic case (internal rotation in the 1,2-dichloroethane molecule), showing how reactions can be inhibited or catalyzed depending on the profile of the molecular dipole. Furthermore, we discuss the absence of resonance effects in the present scenario, which can be understood through its connection to Casimir-Polder forces. Finally, we treat the case of many-molecule strong coupling and find collective modifications of reaction rates if the molecular permanent dipole moments are oriented with respect to the cavity field. |
| first_indexed | 2024-12-21T00:50:54Z |
| format | Article |
| id | doaj.art-657d2aa6950b43bf8a05e5c318d007b1 |
| institution | Directory Open Access Journal |
| issn | 2160-3308 |
| language | English |
| last_indexed | 2024-12-21T00:50:54Z |
| publishDate | 2019-06-01 |
| publisher | American Physical Society |
| record_format | Article |
| series | Physical Review X |
| spelling | doaj.art-657d2aa6950b43bf8a05e5c318d007b12022-12-21T19:21:24ZengAmerican Physical SocietyPhysical Review X2160-33082019-06-019202105710.1103/PhysRevX.9.021057Cavity Casimir-Polder Forces and Their Effects in Ground-State Chemical ReactivityJavier GalegoClàudia ClimentFrancisco J. Garcia-VidalJohannes FeistHere, we present a fundamental study on how the ground-state chemical reactivity of a single molecule can be modified in a QED scenario, i.e., when it is placed inside a nanoscale cavity and there is strong coupling between the cavity field and vibrational modes within the molecule. We work with a model system for the molecule (Shin-Metiu model) in which nuclear, electronic, and photonic degrees of freedom are treated on the same footing. This simplified model allows the comparison of exact quantum reaction rate calculations with predictions emerging from transition state theory based on the cavity Born-Oppenheimer approach. We demonstrate that QED effects are indeed able to significantly modify activation barriers in chemical reactions and, as a consequence, reaction rates. The critical physical parameter controlling this effect is the permanent dipole of the molecule and how this magnitude changes along the reaction coordinate. We show that the effective coupling can lead to significant single-molecule energy shifts in an experimentally available nanoparticle-on-mirror cavity. We then apply the validated theory to a realistic case (internal rotation in the 1,2-dichloroethane molecule), showing how reactions can be inhibited or catalyzed depending on the profile of the molecular dipole. Furthermore, we discuss the absence of resonance effects in the present scenario, which can be understood through its connection to Casimir-Polder forces. Finally, we treat the case of many-molecule strong coupling and find collective modifications of reaction rates if the molecular permanent dipole moments are oriented with respect to the cavity field.http://doi.org/10.1103/PhysRevX.9.021057 |
| spellingShingle | Javier Galego Clàudia Climent Francisco J. Garcia-Vidal Johannes Feist Cavity Casimir-Polder Forces and Their Effects in Ground-State Chemical Reactivity Physical Review X |
| title | Cavity Casimir-Polder Forces and Their Effects in Ground-State Chemical Reactivity |
| title_full | Cavity Casimir-Polder Forces and Their Effects in Ground-State Chemical Reactivity |
| title_fullStr | Cavity Casimir-Polder Forces and Their Effects in Ground-State Chemical Reactivity |
| title_full_unstemmed | Cavity Casimir-Polder Forces and Their Effects in Ground-State Chemical Reactivity |
| title_short | Cavity Casimir-Polder Forces and Their Effects in Ground-State Chemical Reactivity |
| title_sort | cavity casimir polder forces and their effects in ground state chemical reactivity |
| url | http://doi.org/10.1103/PhysRevX.9.021057 |
| work_keys_str_mv | AT javiergalego cavitycasimirpolderforcesandtheireffectsingroundstatechemicalreactivity AT claudiacliment cavitycasimirpolderforcesandtheireffectsingroundstatechemicalreactivity AT franciscojgarciavidal cavitycasimirpolderforcesandtheireffectsingroundstatechemicalreactivity AT johannesfeist cavitycasimirpolderforcesandtheireffectsingroundstatechemicalreactivity |