arXiv subjects

Clàudia Climent

Publications and source records attributed to Clàudia Climent.

5 recordsLinked to original sources

arXiv2026

Chiral vibrational modes and vibrational circular dichroism

The recent interest in chiral phonons in a variety of physical phenomena and their hypothesized role in the chiral-induced spin selectivity effect [Phys. Rev. Research, 5, L022039 (2023)] call for further investigation into the chirality of molecular vibrations. Although molecular chirality has conventionally been quantified using structural properties, recent work has highlighted the role of dynamical response properties as chirality metrics. In this work, we examine an inter-atom helicity pseudoscalar as a complementary measure of vibrational chirality, associated with the vibrational circular dichroism (VCD) intensity in the fixed partial charge (FPC) approximation. This pseudoscalar is translationally and rotationally invariant, can distinguish between opposite enantiomers, and unlike an atomic pseudoscalar measure considered in our earlier work [Phys. Rev. Lett., 133, 268001 (2024)] does not rely on a predefined symmetry axis. For a twisted ethane model as well as several small molecules, this pseudoscalar correlates well with structural descriptors based on the continuous chirality measure. Overall, our results support response-based metrics as a physically meaningful and practically useful characterization of vibrational chirality. Importantly, while the FPC-based VCD estimate provides a useful quantifier of vibrational chirality, we show that it is a rather poor predictor of the actual molecular VCD response because the latter is strongly influenced by the (vibrational configuration-dependent) molecular electronic response.

physics.chem-ph↗

arXiv2023

Heat Transport with a Twist

Despite the desirability of polymers for use in many products due to their flexibility, light weight, and durability, their status as thermal insulators has precluded their use in applications where thermal conductors are required. However, recent results suggest that the thermal conductance of polymers can be enhanced and that their heat transport behaviors may be highly sensitive to nanoscale control. Here we use non-equilibrium molecular dynamics (MD) simulations to study the effect of mechanical twist on the steady-state thermal conductance across multi-stranded polyethylene wires. We find that a highly twisted double-helical polyethylene wire can display a thermal conductance up to three times that of its untwisted form, an effect which can be attributed to a structural transition in the strands of the double helix. We also find that in thicker wires composed of many parallel strands, adding just one twist can increase its thermal conductance by over 30%. However, we find that unlike stretching a polymer wire, which causes a monotonic increase in thermal conductance, the effect of twist is highly non-monotonic, and certain amounts of twist can actually decrease the thermal conductance. Finally, we apply the Continuous Chirality Measure (CCM) in an attempt to explore the correlation between heat conductance and chirality. The CCM is found to correlate with twist as expected, but we attribute the observed heat transport behaviors to structural factors other than chirality.

physics.comp-ph↗

arXiv2023

Kubo-Anderson theory of polariton lineshape

We apply the Kubo-Anderson stochastic theory of molecular spectral lineshape to the case of polaritons formed in the collective strong coupling regime. We investigate both the fast and slow limits of the random frequency modulation of the emitter as well as the intermediate regime and show how the interplay between the characteristic timescales of the cavity and the molecular disorder is expressed in the observed polaritons lineshapes. The analytical solution obtained for the slow limit is valid for any ratio between the inhomogeneous broadening of the molecules and the Rabi splitting, especially relevant for molecular polaritons where these two quantities can be of the same order of magnitude.

physics.chem-ph↗

arXiv2021

Not dark yet: strong light-matter coupling can accelerate singlet fission dynamics

Polaritons are unique hybrid light-matter states that offer an alternative way to manipulate chemical processes and change material properties. In this work we theoretically demonstrate that singlet fission dynamics can be accelerated under strong light-matter coupling. For superexchange-mediated singlet fission, state mixing speeds up the dynamics in cavities when the lower polariton is close in energy to the multiexcitonic triplet-pair state. We show that this effect is more pronounced in non-conventional singlet fission materials in which the energy gap between the bright singlet exciton and the multiexcitonic state is large (> 0.1 eV). In this case, the dynamics is dominated by the polaritonic modes and not by the bare-molecule-like dark states, and additionally, the resonant enhancement due to strong coupling is very robust even for energetically broad molecular states. The present results provide a new strategy to expand the range of suitable materials for efficient singlet fission by making use of strong light-matter coupling.

physics.chem-ph↗

arXiv2019

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 molecule can be modified in a QED scenario, i.e., when it is placed inside a 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 this process, 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 respected to the cavity field. This demonstrates that collective coupling can also provide a mechanism for modifying ground-state chemical reactivity of an ensemble of molecules coupled to a cavity mode.

quant-ph↗