arXiv subjects

Carlos M. Bustamante

Publications and source records attributed to Carlos M. Bustamante.

7 recordsLinked to original sources

arXiv2026

Linear and nonlinear vibrational excitation driven by molecular polaritons

Following our recent numerical study [arXiv:2601.16299 (2026)], we investigate vibrational excitation induced by transient optical driving in molecular ensembles strongly coupled to a cavity mode using the field-driven Holstein--Tavis--Cummings model. We analyze how pulsed excitation redistributes energy among electronic, photonic, and vibrational degrees of freedom in molecular polaritons. Vibrational dynamics are examined over a broad range of pulse durations and intensities within both the single-excitation approximation and a mean-field description of collective light--matter coupling. Despite their distinct formulations and microscopic descriptions, these two approaches yield consistent scaling relations for vibrational excitation. In particular, we disentangle linear and nonlinear contributions to vibrational excitation, which are reflected in distinct quadratic and quartic scaling behaviors with respect to the driving field amplitude (that is, linear and quadratic dependence on the incident pulse intensity). The microscopic origin of the nonlinear component is identified as a polariton-mediated intrapulse stimulated Raman-like process, enabled by a pulse spectral bandwidth large enough to overlap both upper and lower polaritons (rather than a conventional multi-pulse scheme). These results establish a unified framework for understanding vibrational excitation under pulsed polariton driving and provide guidance for the interpretation and control of ultrafast polariton experiments. Discrepancies between the mean-field and single-excitation approaches under certain pulsed conditions are identified and analyzed.

physics.chem-ph↗

arXiv2026

Collective Rabi-driven vibrational activation in molecular polaritons

Molecular polaritons arise from electronic or vibrational strong coupling (ESC and VSC) with confined electromagnetic fields. While these have been widely studied, the influence of electron-nuclear dynamics in driven cavities remains largely unknown. Here, we report a previously unrecognized mechanism of vibrational activation that emerges under collective ESC in driven optical cavities. Using simulations that self-consistently combine Maxwell's equations with quantum molecular dynamics, we show that collective electronic Rabi oscillations coherently drive nuclear motion. This effect is captured using both vibrational wave-packet dynamics in a minimal two-level model and atomistic simulations based on time-dependent density-functional tight-binding theory. Vibrational activation depends non-monotonically on the Rabi frequency and is maximized when the collective polaritonic splitting resonates with a molecular vibrational mode. The mechanism exhibits features consistent with a stimulated Raman-like relaxation mechanism. Our predictions are robust under realistic cavity conditions and provide the conditions in which they could be verified experimentally.

physics.comp-ph↗

arXiv2025

Molecular polariton dynamics in realistic cavities

The large number of degrees of freedom involved in polaritonic chemistry processes considerably restricts the systems that can be described by any ab initio approach, due to the resulting high computational cost. Semiclassical methods that treat light classically offer a promising route for overcoming these limitations. In this work, we present a new implementation that combines the numerical propagation of Maxwell's equations to simulate realistic cavities with quantum electron dynamics at the density functional tight-binding (DFTB) theory level. This implementation allows for the simulation of a large number of molecules described at the atomistic level, interacting with cavity modes obtained by numerically solving Maxwell's equations. By mimicking experimental setups, our approach enables the calculation of transmission spectra, in which we observe the corresponding polaritonic signals. In addition, we have access to local information, revealing complex responses of individual molecules that depend on the number, geometry, position, and orientation of the molecules inside the cavity.

physics.comp-ph↗

arXiv2025

Density-Functional Tight Binding Meets Maxwell: Unraveling the Mysteries of (Strong) Light-Matter Coupling Efficiently

Controlling chemical and material properties through strong light-matter coupling in optical cavities has gained considerable attention over the past decade. However, the underlying mechanisms remain insufficiently understood, and a significant gap persists between experimental observations and theoretical descriptions. This challenge arises from the intrinsically multi-scale nature of the problem, where non-perturbative feedback occurs across different spatial and temporal scales. Collective coupling between a macroscopic ensemble of molecules and a photonic environment, such as Fabry-Perot cavity, can strongly influence the microscopic properties of individual molecules, while microscopic details of the ensemble in turn affect the macroscopic coupling. To address this complexity, we present an efficient computational framework that combines density-functional tight binding (DFTB) with finite-difference time-domain (FDTD) simulations for Maxwell's equations (DFTB+Maxwell). This approach allows for a self-consistent treatment of both the cavity and microscopic details of the molecular ensemble. We demonstrate the potential for this method by tackling several open questions. First, we calculate non-perturbatively two-dimensional spectroscopic observable that directly connect to well-established experimental protocols. Second, we provide local, molecule-resolved information within collectively coupled ensembles, which is difficult to obtain experimentally. Third, we show how cavity designs can be optimized to target specific microscopic applications. Finally, we outline future directions to enhance the predictive power of this framework, including extension to finite temperature, condensed phases, and correlated quantum effects.

physics.chem-ph↗

arXiv2025

Attosecond charge transfer in atomic-resolution scanning tunnelling microscopy

Electrons in atoms and molecules move on attosecond time scales. Deciphering their quantum dynamics in space and time calls for high-resolution microscopy at this speed. While scanning tunnelling microscopy (STM) driven with terahertz pulses has visualized sub-picosecond motion of single atoms, the advent of attosecond light pulses has provided access to the much faster electron dynamics. Yet, combining direct atomic spatial and attosecond temporal resolution remained challenging. Here, we reveal atomic-scale quantum motion of single electrons in attosecond lightwave-driven STM. Near-infrared single-cycle waveforms from phase-controlled optical pulse synthesis steer and clock electron tunnelling. By keeping the thermal load of the tip-sample junction stable, thereby eliminating thermal artifacts, we detect waveform-dependent currents on sub-cycle time scales. Our joint theory-experiment campaign shows that single-cycle near-infrared pulses can drive isolated electronic wave packets shorter than 1 fs. The angstrom-scale decay of the tunnelling current earmarks a fascinating interplay of multi-photon and field-driven dynamics. By balancing these effects, we sharply image a single copper adatom on a silver surface with lightwave-driven currents. This long-awaited fusion of attosecond science with atomic-scale STM makes elementary dynamics of electrons inside atoms, molecules and solids accessible to direct spatio-temporal videography and atom-scale petahertz electronics.

physics.optics↗

arXiv2024

The relevance of degenerate states in chiral polaritonics

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 a parity-conserving/achiral theory is sufficient (e.g. long-wavelength/dipole approximation). This question is non-trivial to answer, since achiral theories (Hamiltonians) still possess chiral solutions. To elucidate this fundamental theoretical question, a simple GaAs quantum ring model is coupled to an effective chiral mode of a single-handedness optical cavity in dipole approximation. The bare matter GaAs quantum ring possesses a non-degenerate ground state and a doubly degenerate first excited state. The chiral or achiral nature (superpositions) of the degenerate excited states remains undetermined for an isolated matter system. However, inside our parity-conserving description of a chiral cavity, we find that the dressed eigenstates automatically (ab-initio) attain chiral character and become energetically discriminated based on the handedness of the cavity. In contrast, the non-degenerate bare matter state (ground state) does not show an energetic discrimination inside a chiral cavity within dipole approximation. Nevertheless, our results suggest that the handedness of the cavity can still be imprinted onto these states (e.g. angular momentum and chiral current densities). Overall, above findings highlight the relevance of degenerate states in chiral polaritonics. In particular, because recent theoretical results for linearly polarized cavities indicate the formation of a frustrated and highly-degenerate electronic ground-state under collective strong coupling conditions, which, likewise, is expected to form in chiral polaritonics and thus could be prone to chiral symmetry breaking effects.

physics.chem-ph↗

arXiv2024

Full minimal coupling Maxwell-TDDFT: an ab initio framework for light-matter phenomena beyond the dipole approximation

We report the first ab initio, non-relativistic QED method that couples light and matter self-consistently beyond the electric dipole approximation and without multipolar truncations. This method is based on an extension of the Maxwell-Pauli-Kohn-Sham approach to a full minimal coupling Hamiltonian, where the space- and time-dependent vector potential is coupled to the matter system, and its back-reaction to the radiated fields is generated by the full current density. The implementation in the open-source Octopus code is designed for massively-parallel multiscale simulations considering different grid spacings for the Maxwell and matter subsystems. Here, we show the first applications of this framework to simulate renormalized Cherenkov radiation of an electronic wavepacket, magnetooptical effects with non-chiral light in non-chiral molecular systems, and renormalized plasmonic modes in a nanoplasmonic dimer. We show that in some cases the beyond-dipole effects can not be captured by a multipolar expansion Hamiltonian in the length gauge. Finally, we discuss further opportunities enabled by the framework in the field of twisted light and orbital angular momentum, inelastic light scattering and strong field physics.

cond-mat.mes-hall↗