Coherent Control with Modified Vacuum Fields

Session

Poster session

12 Aug 2024, 18:00

Albano 3: 5203 - Floor 5 Large Lunch Room (44 seats) (Albano Building 3)

29. A Discrete Truncated Wigner Approximation approach to polariton dynamics

Johannes Schachenmayer (CNRS & University of Strasbourg), Maxence Pandini (CESQ/ISIS, CNRS & University of Strasbourg)

12/08/2024, 18:00

Poster

Experiments in polaritonic chemistry have demonstrated that the collective coupling of molecules to a cavity can modify chemical reactions. These modifications could come from genuine quantum effects and the study of the full quantum dynamics is thus of high interest for such systems. Efficiently computing quantum many-body dynamics has been a very challenging goal and many attempts with...

31. Atomistic resolution simulations of molecules in nanocavities

Emmi Pohjolainen (University of Jyväskylä)

12/08/2024, 18:00

Poster

Discrepancy between atomistic molecular dynamics and experiment can arise, among other things, from the difference in the number of molecules that are considered, making the direct comparison between simulation and experiment often ambiguous. Especially for investigating phenomena that directly depend on the number of molecules, such as strong coupling between light and matter, a meaningful...

30. Coupling Polyatomic Molecules to Lossy Nanocavities: Lindblad versus Schrödinger description

Gábor Halász (University of Debrecen)

12/08/2024, 18:00

Poster

The use of cavities to impact molecular structure and dynamics has become popular. As cavities, in particular plasmonic nanocavities, are lossy and the lifetime of their modes can be very short, their lossy nature must be incorporated into the calculations. The Lindblad master equation isommonly considered as an appropriate tool to describe this lossy nature. This approach requires the...

38. Extending the Tavis-Cummings model for molecular ensembles - Exploring the effects of dipole self energies and static dipole moments

Lucas Garcia Borges (Stockholm University)

12/08/2024, 18:00

Poster

Strong coupling of organic molecules to the vacuum field of a nanoscale cavity can be used to modify their chemical and physical properties. We extend the Tavis-Cummings model for molecular ensembles and show that the often neglected interaction terms arising from the static dipole moment and the dipole self-energy are essential for a correct description of the light-matter interaction in...

11. Insights into the mechanisms of optical cavity-modified ground-state chemical reactions

Yaling Ke (ETH Zürich)

12/08/2024, 18:00

Poster

In this presentation, we employ a numerically exact, fully quantum dynamical approach to systematically investigate the mechanisms underlying the rate modification of ground-state chemical reactions inside an infrared optical cavity under the vibrational strong coupling regime.

First of all, we've revealed that static quantum features such as zero-point energy and pure tunneling effects...

39. Interaction between polyatomic molecules on layered surfaces beyond the dipole approximation

Hsiao-Han Chuang (Max Planck Institute for the Physics of Complex Systems)

12/08/2024, 18:00

Poster

For aggregates of molecular monomers above layered surfaces, the dipole approximation breaks down when the distance between monomers and surfaces is less than several nanometers. To overcome this problem, we employ macroscopic quantum electrodynamics and use the complete transition current density of the individual monomers. Within this framework, the resulting Master Equation for the...

26. Nucleophilicity of Water and Alcohols: Measuring Kinetics under Vibrational Strong Coupling.

Cyprien Muller (University of Strasbourg)

12/08/2024, 18:00

Poster

Vibrational Strong Coupling (VSC) has recently been shown to alter the rates and selectivity of polar chemical reactions –reactions in which electrophiles and nucleophiles combine. However, measuring reliable reaction kinetics under VSC remains an important challenge which hinders our ability to know which specific elementary properties of polar reactions are affected by VSC. We herein set out...

34. Towards new photochemistry with quantum electrodynamics coupled cluster theory

Sara Angelico (Norwegian University of Science and Technology (NTNU))

12/08/2024, 18:00

Poster

When light and matter strongly interact, polaritonic states with mixed electronic and photonic character emerge. As a consequence, new photochemical pathways become available under strong coupling conditions. In order to get insight on the mechanism underlying these modifications, theoretical studies using accurate ab initio methods are fundamental. In particular, Quantum Electrodynamics -...

36. Training machine learning potentials for studying dynamics under vibrational strong coupling

Esmée Berger (Chalmers University of Technology)

12/08/2024, 18:00

Poster

Machine learning potentials have recently been used to simulate chemical dynamics under vibrational strong coupling, in order to gain greater insight into the underlying microscopic mechanisms [1]. These machine learning potentials are trained on data from density functional theory and are used to evaluate the forces during molecular dynamics simulations, which facilitates atomistic insight...

21. Ultra-strong light matter coupling with itinerant electrons

Marios Michael (Max Planck Institute for the Structure and Dynamics of matter)

12/08/2024, 18:00

Poster

The interaction between matter and the quantum fluctuations of light in cavities can lead to novel exotic states of matter. Previous theoretical investigations into this area have produced conflicting outcomes, creating obstacles for further research. In this talk, I pinpoint the source of these discrepancies to the inherently divergent nature of local quantum light fluctuations in vacuum. To...

5. Ultrafast and Coherent Dynamics in Strong Coupled Light-Matter Systems through Two-Dimensional Electronic Spectroscopy (2DES)

Federico Toffoletti (University of Padova)

12/08/2024, 18:00

Poster

The ability to manipulate light at the nanoscale is greatly enhanced by the tremendous progress done in the field of plasmonic nanoparticles. Their high versatility enables the confinement and control of very strong electric fields, making these nanosystems ideal candidates for polaritonic states formation when combined with strong quantum emitters, such as molecular excitons. The resulting...

15. Understanding the cavity Born–Oppenheimer approximation

Marit Fiechter (ETH Zürich)

12/08/2024, 18:00

Poster

Experiments have demonstrated that vibrational strong coupling between molecular vibrations and light modes can significantly change molecular properties, such as ground-state reactivity. Theoretical studies toward the origin of this exciting observation can roughly be divided into two categories. On the one hand, there are studies based on Hamiltonians that simply couple a molecule to a...

40. Linear optical properties of organic microcavity polaritons with non-Markovian quantum state diffusion

Dr Kimmo Luoma (University of Turku)

Poster

In this work we present the numerically exact non-Markovian Quantum State Diffusion approach for organic microcavity polaritons. In this approach we are able to solve the total Schrödinger equation for the molecular excitons, cavity mode and molecular vibrations which acts as an environment for the polariton system. We compute the linear absorption and emission spectra and compare our results...

37. Simulating Quantum Effects in Electronic Strong Coupling We investigate and compare simulations of the collective coupling of an ensemble of molecules to a cavity field using semi-classical hybrid quantum mechanics/molecular mechanics (QM/MM) and multi-configuration time-dependent Hartree (MCTDH) approaches. We aim to validate the semi-classical molecular dynamics (MD) and assess the role of quantum effects in the relaxation processes. Initially, we considered a diatomic CO molecule and optimized its equilibrium geometry at the electronic ground state using the CCSD/aug-cc-pVDZ level of theory with the G09 program. The first six singlet low-lying electronic states were calculated using the CASSCF (14,10) ab initio quantum chemistry method along the CO internuclear distance. We then constructed the Tavis-Cummings model Hamiltonian by considering the ground and first excited electronic states of the CO molecule within the rotating wave approximation. Simulations were performed using both QM/MM and MCTDH approaches. Our simulations show that the results are qualitatively in agreement when a single CO molecule is coupled to the cavity mode. The project involving multiple molecules is still in progress.

Dr Arun Kanakati (University of Jyvaskyla), Gerrit Groenhof (University of Jyvaskyla)

Poster