Collective Polaritonic Effects on Chemical Dynamics Suppressed by Disorder

• URL: http://arxiv.org/abs/2308.03954v4
• Date: Fri, 5 Apr 2024 20:32:16 GMT
• Title: Collective Polaritonic Effects on Chemical Dynamics Suppressed by Disorder
• Authors: Juan B. Pérez-Sánchez, Federico Mellini, Noel C. Giebink, Joel Yuen-Zhou,
• Abstract summary: We present a powerful formalism, disordered collective dynamics using truncated equations (d-CUT-E) Using d-CUT-E we conclude that strong coupling, as evaluated from linear optical spectra, can be a poor proxy for polariton chemistry.
• Score: 0.0
• License: http://arxiv.org/licenses/nonexclusive-distrib/1.0/
• Abstract: We present a powerful formalism, disordered collective dynamics using truncated equations (d-CUT-E), to simulate the ultrafast quantum dynamics of molecular polaritons in the collective strong coupling regime, where a disordered ensemble of $N\gg10^{6}$ molecules couples to a cavity mode. Notably, we can capture this dynamics with a cavity hosting a single \textit{effective} molecule with $\sim N_{bins}$ electronic states, where $N_{bins}\ll N$ is the number of bins discretizing the disorder distribution. Using d-CUT-E we conclude that strong coupling, as evaluated from linear optical spectra, can be a poor proxy for polariton chemistry. For highly disordered ensembles, total reaction yield upon broadband excitation is identical to that outside of the cavity, while narrowband excitation produces distinct reaction yields solely due to differences in the initial states prepared prior to the reaction.

Related papers

• CUT-E as a $1/N$ expansion for multiscale molecular polariton dynamics [0.0]
  Molecular polaritons arise when the collective coupling between an ensemble of $N$ molecules and an optical mode exceeds individual photon and molecular linewidths. We provide a novel derivation of CUT-E based on recently developed bosonization techniques. We lay down its connections with $1/N$ expansions that are ubiquitous in other fields of physics, and present previously unexplored key aspects of this formalism.
  arXiv  Detail & Related papers  (2024-10-18T04:56:48Z)
• Analytic Model for Molecules Under Collective Vibrational Strong Coupling in Optical Cavities [0.9824636175880032]
  We present a model system consisting of an ensemble of N molecules under vibrational strong coupling (VSC) A priori no harmonic approximation is imposed for the inter-nuclear interactions. We highlight that anharmonic intra-molecular interactions might become essential for the formation of local strong coupling effects.
  arXiv  Detail & Related papers  (2024-01-29T18:13:43Z)
• Exploring the impact of vibrational cavity coupling strength on ultrafast CN + $c$-C$_6$H$_{12}$ reaction dynamics [45.46706627196389]
  We study the ultrafast dynamics of CN radicals interacting with a cyclohexane and chloroform. Reaction rates remain unchanged for all extracavity, on resonance, and off-resonance cavity coupling conditions.
  arXiv  Detail & Related papers  (2023-10-29T19:46:42Z)
• $N$ Scaling of Large-Sample Collective Decay in Inhomogeneous Ensembles [44.99833362998488]
  We experimentally study collective decay of an extended disordered ensemble of $N$ atoms inside a hollow-core fiber. We observe up to $300$-fold enhanced decay rates, strong optical bursts and a coherent ringing.
  arXiv  Detail & Related papers  (2023-07-21T14:43:29Z)
• Cavity-Catalyzed Hydrogen Transfer Dynamics in an Entangled Molecular Ensemble under Vibrational Strong Coupling [0.0]
  We numerically solve the Schr"odinger equation to study the cavity-induced quantum dynamics in an ensemble of molecules. We show that the cavity indeed enforces hydrogen transfer from an enol to an enethiol configuration with transfer rates significantly increasing with light-matter interaction strength. A non-trivial dependence of the dynamics on ensemble size is found, clearly beyond scaled single-molecule models.
  arXiv  Detail & Related papers  (2023-01-10T16:58:57Z)
• Collective dynamics Using Truncated Equations (CUT-E): simulating the collective strong coupling regime with few-molecule models [0.0]
  We exploit permutational symmetries to drastically reduce the computational cost of textitab-initio quantum dynamics simulations for large $N$. We show that addition of $k$ extra effective molecules is enough to account for phenomena whose rates scale as $mathcalO(N-k)$.
  arXiv  Detail & Related papers  (2022-09-11T22:49:29Z)
• Computational Insights into Electronic Excitations, Spin-Orbit Coupling Effects, and Spin Decoherence in Cr(IV)-based Molecular Qubits [63.18666008322476]
  We provide insights into key properties of Cr(IV)-based molecules aimed at assisting chemical design of efficient molecular qubits. We find that the sign of the uniaxial zero-field splitting (ZFS) parameter is negative for all considered molecules. We quantify (super)hyperfine coupling to the $53$Cr nuclear spin and to the $13C and $1H nuclear spins.
  arXiv  Detail & Related papers  (2022-05-01T01:23:10Z)
• Generalization of the Tavis-Cummings model for multi-level anharmonic systems: insights on the second excitation manifold [0.0]
  This work contrasts predictions from the Tavis-Cummings (TC) model, in which the material is a collection of two-level systems. We simplify the brute-force diagonalization of a gigantic $N2times N2$ Hamiltonian. We find resonant conditions between bipolaritons and anharmonic transitions where two-photon absorption can be enhanced.
  arXiv  Detail & Related papers  (2022-02-03T06:33:42Z)
• Intrinsic mechanisms for drive-dependent Purcell decay in superconducting quantum circuits [68.8204255655161]
  We find that in a wide range of settings, the cavity-qubit detuning controls whether a non-zero photonic population increases or decreases qubit decay Purcell. Our method combines insights from a Keldysh treatment of the system, and Lindblad theory.
  arXiv  Detail & Related papers  (2021-06-09T16:21:31Z)
• Deterministic single-atom source of quasi-superradiant $N$-photon pulses [62.997667081978825]
  Scheme operates with laser and cavity fields detuned from the atomic transition by much more than the excited-state hyperfine splitting. This enables reduction of the dynamics to that of a simple, cavity-damped Tavis-Cummings model with the collective spin determined by the total angular momentum of the ground hyperfine level.
  arXiv  Detail & Related papers  (2020-12-01T03:55:27Z)
• Anisotropy-mediated reentrant localization [62.997667081978825]
  We consider a 2d dipolar system, $d=2$, with the generalized dipole-dipole interaction $sim r-a$, and the power $a$ controlled experimentally in trapped-ion or Rydberg-atom systems. We show that the spatially homogeneous tilt $beta$ of the dipoles giving rise to the anisotropic dipole exchange leads to the non-trivial reentrant localization beyond the locator expansion.
  arXiv  Detail & Related papers  (2020-01-31T19:00:01Z)

This list is automatically generated from the titles and abstracts of the papers in this site.

This site does not guarantee the quality of this site (including all information) and is not responsible for any consequences.