This Perspective provides a brief introduction into the theoretical complexity of polaritonic chemistry, which emerges from hybrid nature strongly coupled light-matter states. To tackle this complexity, importance ab initio methods is highlighted. Based on those, novel ideas and research avenues are developed with respect to quantum collectivity, as well for resonance phenomena immanent in reaction rates under vibrational strong coupling. Indeed, fundamental questions arise about mesoscopic...

We demonstrate that collective vibrational strong coupling of molecules in thermal equilibrium can give rise to significant local electronic polarizations the thermodynamic limit. do so by first showing full nonrelativistic Pauli–Fierz problem an ensemble strongly coupled dilute-gas limit reduces cavity Born–Oppenheimer approximation a cavity–Hartree equation for structure. Consequently, each individual molecule experiences self-consistent dipoles all other molecules, which amount...

A fundamental question in the field of polaritonic chemistry is whether collective coupling implies local modifications chemical properties scaling with ensemble size. Here we demonstrate from first-principles that an impurity present a collectively coupled features such locally modifications. In particular, find formation novel dark state for nitrogen dimer chain variable size, whose are altered considerably at due to its embedding environment. Our simulations unify theoretical predictions...

Experimental studies indicate that optical cavities can affect chemical reactions through either vibrational or electronic strong coupling and the quantized cavity modes. However, current understanding of interplay between molecules confined light modes is incomplete. Accurate theoretical models take into account intermolecular interactions to describe ensembles are therefore essential understand mechanisms governing polaritonic chemistry. We present an ab initio Hartree-Fock ansatz in...

Despite recent numerical evidence, one of the fundamental theoretical mysteries polaritonic chemistry is how and if collective strong coupling can induce local changes electronic structure to modify chemical properties. Here we present nonperturbative analytic results for a model system consisting an ensemble <a:math xmlns:a="http://www.w3.org/1998/Math/MathML"><a:mi>N</a:mi></a:math> harmonic molecules under vibrational (VSC) that alters our understanding this question. By applying cavity...

In recent years tremendous progress in the field of light-matter interactions has unveiled that strong coupling to modes an optical cavity can alter chemistry even at room temperature. Despite these impressive advances, many fundamental questions cavities remain unanswered. This is also due a lack exact results be used validate and benchmark approximate approaches. this work we provide such reference calculations from diagonalization Pauli-Fierz Hamiltonian long-wavelength limit with...

Replica-exchange enveloping distribution sampling (RE-EDS) allows the efficient estimation of free-energy differences between multiple end-states from a single molecular dynamics (MD) simulation. In EDS, reference state is sampled, which can be tuned by two types parameters, i.e., smoothness parameters(s) and energy offsets, such that all are sufficiently sampled. However, choice these parameters not trivial. Replica exchange (RE) or parallel tempering widely applied technique to enhance...

In molecular dynamics (MD) simulations, free-energy differences are often calculated using free energy perturbation or thermodynamic integration (TI) methods. However, both techniques only suited to calculate between two end states. Enveloping distribution sampling (EDS) presents an attractive alternative that allows multiple in a single simulation. EDS, reference state is simulated which "envelopes" the The challenge of this methodology determination optimal reference-state parameters...

We demonstrate that collective vibrational strong coupling of molecules in thermal equilibrium can give rise to significant local electronic polarizations the thermodynamic limit. do so by first showing full non-relativistic Pauli-Fierz problem an ensemble strongly-coupled dilute-gas limit reduces cavity Born-Oppenheimer approximation a cavity-Hartree equation for structure. Consequently, each individual molecule experiences self-consistent dipoles all other molecules, which amount...

An extension of the Nosé–Hoover thermostat equation for molecular dynamics (MD) simulation is introduced, which perturbs fast degrees freedom out canonical equilibrium, while preserving average temperature system.

Experimental determination of the absolute stereochemistry chiral molecules has been a fundamental challenge in natural sciences for decades. Vibrational circular dichroism (VCD) spectroscopy represents an attractive alternative to traditional methods like X-ray crystallography due use solution. The interpretation measured VCD spectra and thus assignment configuration relies on quantum-mechanical calculations. While such calculations are straightforward rigid with single conformation, need...

The first numerically exact simulation of a full ab initio molecular quantum system (HD

In this review we present the theoretical foundations and first principles frameworks to describe quantum matter within electrodynamics (QED) in low-energy regime. Having a rigorous fully quantized description of interacting photons, electrons nuclei/ions, from weak strong light-matter coupling regimes, is pivotal for detailed understanding emerging fields polaritonic chemistry cavity materials engineering. The use avoids ambiguities problems stemming using approximate models based on...

Reaction-field (RF) methods have been extensively used in molecular dynamics simulations to efficiently compute long-range electrostatic interactions. They assume a continuous dielectric medium outside certain cutoff, which has shown be reasonable approximation many cases. However, lattice sum or fast multipole are nowadays often instead, treat interactions explicitly but may introduce different artefacts. In the following work, major issue of RFs is addressed, i.e., their inability account...

The difference in absorption of left and right circularly polarized light by chiral molecules can be described the Rosenfeld equation for isotropic samples. It allows assignment absolute stereochemistry comparing experimental computationally derived spectra. Despite simple form equation, its evaluation infrared regime remained challenging, as contribution from magnetic dipole operator is zero within Born-Oppenheimer (BO) approximation. In order to resolve this issue, "beyond BO" theories had...

Abstract. In the 1950s and 1960s, specific radionuclides were released into atmosphere as a result of nuclear weapons testing. This radioactive fallout left its signature on accumulated layers glaciers worldwide, thus providing tracer for ice particles traveling within gravitational flow being ablation zone. For surface dating purposes, we analyze here activity 239Pu, 240Pu 236U derived from more than 200 samples collected along five flowlines at Gauligletscher, Switzerland. It was found...

Analytical results are presented for a model system consisting of an ensemble N molecules under vibrational strong coupling (VSC). The single bare molecular is composed one effective electron, which couples harmonically to multiple nuclei. A priori no harmonic approximation imposed the inter-nuclear interactions. Within cavity Born-Oppenheimer partitioning, i.e., when assuming classical nuclei and displacement field coordinates, dressed N-electron problem can be solved analytically in dilute...

In this work we explore theoretically whether a parity-violating/chiral light-matter interaction is required to capture all relevant aspects of chiral polaritonics or if parity-conserving/achiral theory sufficient (e.g. long-wavelength/dipole approximation). This question non-trivial answer, since achiral theories (Hamiltonians) still possess solutions. To elucidate fundamental theoretical question, simple GaAs quantum ring model coupled an effective mode single-handedness optical cavity in...

Polaritonic chemistry has garnered increasing attention in recent years due to pioneering experimental results, which show that site- and bond-selective at room temperature is achievable through strong collective coupling field fluctuations optical cavities. Despite these notable strides, the underlying theoretical mechanisms remain unclear. In this focus review, we highlight a fundamental link between seemingly unrelated fields of polaritonic spin glasses, exploring its profound...

In this work, we theoretically explore whether a parity-violating/chiral light–matter interaction is required to capture all relevant aspects of chiral polaritonics or if parity-conserving/achiral theory sufficient (e.g., long-wavelength/dipole approximation). This question non-trivial answer since achiral theories (Hamiltonians) still possess solutions. To elucidate fundamental theoretical question, simple GaAs quantum ring model coupled an effective mode single-handedness optical cavity in...

<ns4:p><ns4:bold>Background: </ns4:bold>Molecular dynamics (MD) simulations have become an important tool to provide insight into molecular processes involving biomolecules such as proteins, DNA, carbohydrates and membranes. As these cover a wide range of time scales, multiple time-step integration methods are often employed increase the speed MD simulations. For example, in twin-range (TR) scheme, nonbonded forces within long-range cutoff split short-range contribution updated every step...

<ns4:p><ns4:bold>Background:</ns4:bold>Molecular dynamics (MD) simulations have become an important tool to provide insight into molecular processes involving biomolecules such as proteins, DNA, carbohydrates and membranes. As these cover a wide range of time scales, multiple time-step integration methods are often employed increase the speed MD simulations. For example, in twin-range (TR) scheme, nonbonded forces within long-range cutoff split short-range contribution updated every step...

Abstract. In the 1950s and '60s, specific radionuclides were released into atmosphere as a result of nuclear weapons testing. This radioactive fallout left its signature on accumulated layers glaciers worldwide, thus providing tracer for ice particles traveling within gravitational flow being ablation zone. For surface dating purposes, we analyze here activity 239Pu, 240Pu 236U derived from more than 200 samples collected along five flowlines at Gauligletscher, Switzerland. It was found that...