arXiv subjects

Nguyen Thanh Phuc

Publications and source records attributed to Nguyen Thanh Phuc.

At least 19 recordsLinked to original sources

arXiv2026

Variational Polaron Theory for Ground States of Strongly Coupled Light-Matter and Electron-Phonon Systems

Strong light-matter and electron-phonon coupling generate ground states dressed by virtual bosonic excitations, making bare-state truncations and perturbative treatments unreliable in the ultrastrong-coupling regime. We introduce a nonperturbative variational ground-state framework based on a state-dependent polaron transformation, combined with a product-state ansatz and a second-order perturbative correction for residual matter-boson entanglement. We show that the optimized transformed frame becomes asymptotically decoupled at infinite coupling, because the leading linear coupling is canceled while off-diagonal matter transitions are suppressed by displaced-oscillator overlaps. The approach is asymptotically correct in both weak- and strong-coupling limits and remains accurate in the intermediate regime, where fixed polaron transformations are least reliable. Dicke-model benchmarks reproduce ground-state energies, fidelities, and the superradiant transition, with second-order energy errors below 0.2%. Holstein-model benchmarks yield errors below 0.5% and clarify how translational symmetry affects wave-function quality. This dressed-basis framework enables nonperturbative modeling of strongly coupled light-matter and electron-phonon systems.

physics.chem-ph↗

arXiv2026

Molecular Electron Transfer in Optical Cavities: From Excitonic to Vibronic Polaritons

Strong coupling between molecular excitations and quantized electromagnetic fields in optical cavities provides a powerful means to control the physical and chemical properties of molecular systems. Here, we study electron transfer (ET) dynamics in cavity-coupled molecules using the numerically exact hierarchical equations of motion (HEOM) method, which captures nonperturbative and non-Markovian effects beyond standard perturbative theories. We identify distinct resonance and collective effects associated with polariton formation and show that the ET rate saturates in the strong-coupling regime, a feature not captured by perturbative approaches. We further extend the cavity-modified ET model by incorporating the nuclear-coordinate dependence of molecular electric dipole moments, which gives rise to a three-body interaction involving molecular electronic and vibrational degrees of freedom and cavity photons. This vibronic polariton formation leads to non-monotonic, oscillatory dependencies of the ET rate on the light-matter coupling strength and cavity frequency, which we attribute to quantum interference among multiple transfer pathways. These findings establish cavity-modified electron transfer as a multichannel quantum process governed by the interplay of electronic, vibrational, and photonic degrees of freedom.

physics.chem-ph↗

arXiv2024

Semiclassical Truncated-Wigner-Approximation Theory of Molecular Exciton-Polariton Dynamics in Optical Cavities

Molecular exciton polaritons are hybrid states resulting from the strong coupling of molecular electronic excitations with an optical cavity mode, presenting a promising approach for controlling photophysical and photochemical properties in molecular systems. In this study, we develop a semiclassical theory for molecular exciton-polariton dynamics using the truncated Wigner approximation (TWA) to explore the collective behavior of molecular electronic excited states under strong light-matter coupling. Our approach expands the previously developed TWA theory for molecular vibration-polariton dynamics (J. Chem. Theory Comput. 2024, 20, 3019--3027) by incorporating semiclassical treatment of quantum coherence between ground and excited molecular states. We initially apply the TWA theory to a simplified system of molecules modeled as two-level (spin-1/2) systems, omitting vibronic coupling. The semiclassical results derived from applying the TWA to single-spin operators demonstrate excellent agreement with full quantum dynamic simulations in systems with a sufficiently large number of molecules. Lastly, the TWA theory is extended to incorporate molecular vibronic coupling, revealing the dynamic polaron decoupling effect, where quantum coherence between molecular excitations is preserved under strong light-matter coupling.

physics.chem-ph↗

arXiv2024

Semiclassical truncated-Wigner-approximation theory of molecular-vibration-polariton dynamics in optical cavities

It has been experimentally demonstrated that molecular-vibration polaritons formed by strong coupling of a molecular vibration to an infrared cavity mode can significantly modify the physical properties and chemical reactivity of various molecular systems. However, a complete theoretical understanding of the underlying mechanisms of the modifications remains elusive due to the complexity of the hybrid system, especially the collective nature of polaritonic states in systems containing many molecules. We develop here the semiclassical theory of molecular-vibration-polariton dynamics based on the truncated Wigner approximation (TWA) that is tractable in large molecular systems and simultaneously captures the quantum character of photons in the optical cavity. The theory is then applied to investigate the nuclear quantum dynamics of a system of identical diatomic molecules having the ground-state Morse potential and strongly coupled to an infrared cavity mode in the ultrastrong coupling regime. The validity of TWA is examined by comparing it with the fully quantum dynamics of a single-molecule system for two different initial states in the dipole and Coulomb gauges. For the initial tensor-product ground state in the dipole gauge, which corresponds to a light-matter entangled state in the Coulomb gauge, the collective and resonance effects of molecular-vibration-polariton formation on the nuclear dynamics are observed in a system of many molecules.

physics.chem-ph↗

arXiv2023

Floquet-engineered chiral-induced spin selectivity

The control of electron spin, which is crucial to the stability of matter, offers new possibilities for manipulating the properties of molecules and materials with potential applications in spintronics and chemical reactions. Recent experiments have demonstrated that electron transmission through chiral molecules depends on the electron spin orientation, a phenomenon known as chiral-induced spin selectivity (CISS). In this study, we show that CISS can be observed in achiral systems driven by an external circularly polarized laser field in the framework of Floquet engineering. By using the Floquet theory for a time-periodically driven system to investigate spin-dependent electron transport in a two-terminal setup, we demonstrate that the spin polarization can approach unity if the light intensity is sufficiently strong, the rate of dephasing is sufficiently small, and the average chemical potential of the two leads is within an appropriate range of values, which is narrow because of the high frequency of the laser field. To obtain a wider range of energies for large spin polarization, a combination of chiral molecules and light-matter interactions is considered and the spin polarization of electrons transported through a helical molecule driven by a laser field is evaluated.

cond-mat.mes-hall↗

arXiv2022

Chiral cavity induced spin selectivity

Chiral-induced spin selectivity (CISS) is a phenomenon in which electron spins are polarized as they are transported through chiral molecules, and the spin polarization depends on the handedness of the chiral molecule. In this study, we show that spin selectivity can be realized in achiral materials by coupling electrons to a single mode of a chiral optical cavity. By investigating spin-dependent electron transport using the nonequilibrium Green's function approach, the spin polarization in a two-terminal setup is demonstrated to approach unity if the rate of dephasing is sufficiently small and the average chemical potential of the two leads is within an appropriate range of values, which is narrow because of the high frequency of the cavity mode. To obtain a wider range of energies for a large spin polarization, we propose to combine the CISS in chiral molecules with the light-matter interactions. For demonstration, the spin polarization of electrons transported through a helical molecule strongly coupled to a chiral cavity mode is evaluated.

cond-mat.mes-hall↗

arXiv2022

Bose enhancement of excitation-energy transfer with molecular-exciton-polariton condensates

Room-temperature Bose--Einstein condensates (BECs) of exciton polaritons have been realized in organic molecular systems owing to the strong light--matter interaction, strong exciton binding energy, and low effective mass of a polaritonic particle. These molecular-exciton-polariton BECs have demonstrated their potential in nonlinear optics and optoelectronic applications. In this study, we demonstrate that molecular-polariton BECs can be utilized for Bose enhancement of excitation-energy transfer (EET) in a molecular system with an exciton donor coupled to a group of exciton acceptors that are further strongly coupled to a single mode of an optical cavity. Similar to the stimulated emission of light in which photons are bosonic particles, a greater rate of EET is observed if the group of acceptors is prepared in the exciton-polariton BEC state than if the acceptors are initially either in their electronic ground states or in a normal excited state with an equal average number of molecular excitations. The Bose enhancement also manifests itself as the growth of the EET rate with an increasing number of exciton polaritons in the BEC. Finally, a permutation-symmetry-based approach to suppress the EET to the huge manifold of dark states in the acceptor group is proposed to facilitate the Bose-enhanced EET to the polariton BEC.

physics.chem-ph↗

arXiv2021

Superreaction: the collective enhancement of a reaction rate by molecular polaritons in the presence of energy fluctuations

Recent experiments have demonstrated that molecular polaritons, hybrid states of light and matter formed by the strong coupling between molecular electronic or vibrational excitations and an optical cavity, can substantially modify the physical and chemical properties of molecular systems. Here, we show that, by exploiting the collective character of molecular polaritons in conjunction with the effect of polaron decoupling, i.e., the suppression of environmental influence on the polariton, a superreaction can be realized, involving a collective enhancement of charge or excitation-energy transfer reaction rate in a system of donors all coupled to a common acceptor. This effect is analogous to the phenomenon of superradiation. Since the polariton is a superposition state of excitations of all the molecules coupled to the cavity, it is vulnerable to the effect of decoherence caused by energy fluctuations in molecular systems. Consequently, in the absence of a strong light-matter interaction, the reaction rate decreases significantly as the number of molecules increases, even if the system starts from the polariton state. By turning on the light-matter interaction, the dynamic behavior of the system changes dramatically, and the reaction rate increases with the number of molecules, as expected for a superreaction. The underlying mechanism is shown to be the enhancement of quantum coherence between different donors as the light-matter interaction becomes stronger.

physics.chem-ph↗

arXiv2020

Direct and ultrafast probing of quantum many-body interaction and Mott-insulator transition through coherent two-dimensional spectroscopy

Interactions between particles in quantum many-body systems play a crucial role in determining the electric, magnetic, optical, and thermal properties of the system. The recent progress in the laser-pulse technique has enabled the manipulations and measurements of physical properties on ultrafast timescales. Here, we propose a method for the direct and ultrafast probing of quantum many-body interaction through coherent two-dimensional (2D) spectroscopy. Up to a moderate interaction strength, the inter-particle interaction manifests itself in the emergence of off-diagonal peaks in the 2D spectrum before all the peaks coalesce into a single diagonal peak as the system approaches the Mott-insulating phase in the strongly interacting regime. The evolution of the 2D spectrum as a function of the time delay between the second and third laser pulses can provide important information on the ultrafast time variation of the interaction.

cond-mat.str-el↗

arXiv2020

Controlling the nonadiabatic electron-transfer reaction rate through molecular-vibration polaritons in the ultrastrong coupling regime

Recent experiments showed that the chemical reaction rate is modified, either increased or decreased, by strongly coupling a nuclear vibration mode to the single mode of an optical cavity. Herein we investigate how the rate of an electron-transfer reaction depends on the molecule-cavity coupling in the ultrastrong coupling regime, where the coupling strength is comparable in magnitude with both the vibrational and the cavity frequencies. We found two main factors that determine the modification of the reaction rate: the relative shifts of the energy levels induced by the coupling and the mixing of the ground and excited states of molecular vibration in the ground state of the hybrid molecule-plus-cavity system through which the Franck-Condon factor between the initial and final states of the transition is altered. The former is the dominant factor if the molecule-cavity coupling strengths for the reactant and product states differ significantly from each other and gives rise to an increase in the reaction rate over a wide range of system's parameters. The latter dominates if the coupling strengths and energy levels of the reactant and product states are close to each other and it leads to a decrease in the reaction rate. The effect of the mixing of molecular vibrational states on the reaction rate is, however, suppressed in a system containing a large number of molecules due to the collective nature of the resulting polariton, and thus should be observed in a system containing a small number of molecules. In contrast, the effect of the relative shifts of the energy levels should be essentially independent of the number of molecules coupled to the cavity.

physics.chem-ph↗

arXiv2019

Precise determination of excitation energies in condensed-phase molecular systems based on exciton-polariton measurements

The precise determination of the excitation energies in condensed-phase molecular systems is important for understanding system-environment interactions as well as for the prerequisite input data of theoretical models used to study the dynamics of the system. The excitation energies are usually determined by fitting of the measured optical spectra that contain broad and unresolved peaks as a result of the thermally random dynamics of the environment. Herein, we propose a method for precise energy determination by strongly coupling the molecular system to an optical cavity and measuring the energy of the resulting polariton. The effect of thermal fluctuations induced by the environment on the polariton is also investigated, from which a power scaling law relating the polariton's linewidth to the number of molecules is obtained. The power exponent gives important information about the environmental dynamics.

cond-mat.mes-hall↗

arXiv2019

Control of Quantum Dynamics of Electron Transfer in Molecular Loop Structures: Spontaneous Breaking of Chiral Symmetry under Strong Decoherence

Manipulation of quantum systems is the basis for many promising quantum technologies. However, how quantum mechanical principles can be used to manipulate the dynamics of quantum dissipative systems remains unanswered because of strong decoherence effects arising from interaction with the surrounding environment. In this work, we demonstrate that electron transfer dynamics in molecular loop structures can be manipulated with the use of Floquet engineering by applying a laser field. Despite strong dephasing, the system's dynamics spontaneously breaks the chiral symmetry of the loop in a controllable fashion, followed by the generation of a robust steady-state electronic current without an external voltage. An exponential scaling law that relates the magnitude of the current to the system-environment coupling strength is revealed numerically. The breaking of chiral symmetry and the consequent controllable unidirectional flow of electrons could be employed to construct functional molecular electronic circuits.

cond-mat.mes-hall↗

arXiv2018

Many-body spin Hall effect with space-inversion symmetry

In contrast to the ordinary spin Hall effect (SHE), which is a single-body phenomenon caused by the spin-orbit interaction (SOI), we propose amany-body SHE induced by the dipole-dipole interaction (DDI) between particles and demonstrate it in a system of ultracold magnetic atoms. While the SOI usually requires the breaking of space-inversion symmetry, the DDI preserves it. The many-body SHE can, in principle, be observed in a wide range of systems with large dipole moments and offers a powerful tool to generate spin currents, an essential ingredient in spintronics and atomtronics.

cond-mat.quant-gas↗

arXiv2018

Control of Excitation Energy Transfer in Condensed Phase Molecular Systems by Floquet Engineering

Excitation energy transfer (EET) is one of the most important processes in both natural and artificial chemical systems including, for example, photosynthetic complexes and organic solar cells. The EET rate, however, is strongly suppressed when there is a large difference in the excitation energy between the donor and acceptor molecules. Here, we demonstrate both analytically and numerically that the EET rate can be greatly enhanced by periodically modulating the excitation energy difference. The enhancement of EET by using this Floquet engineering, in which the system's Hamiltonian is made periodically time-dependent, turns out to be efficient even in the presence of strong fluctuations and dissipations induced by the coupling with a huge number of dynamic degrees of freedom in the surrounding molecular environments. As an effect of the environment on the Floquet engineering of EET, the optimal driving frequency is found to depend on the relative magnitudes of the system and environment's characteristic time scales with an observed frequency shift when moving from the limit of slow environmental fluctuations (inhomogeneous broadening limit) to that of fast fluctuations (homogeneous broadening limit).

physics.chem-ph↗

arXiv2016

Geometrically Frustrated Coarsening Dynamics in Spinor Bose-Fermi Mixtures

Coarsening dynamics theory has successfully described the equilibration of a broad class of systems.By studying the relaxation of a periodic array of microcondensates immersed in a Fermi gas which can mediate long-range spin interactions to simulate frustrated classical magnets, we show that coarsening dynamics can be suppressed by geometrical frustration. The system is found to eventually approach a metastable state which is robust against random field noise and characterized by finite correlation lengths with the emergence of topologically stable Z2 vortices. We find universal scaling laws with no thermal-equilibrium analog that relate the correlation lengths and the number of vortices to the degree of frustration in the system.

cond-mat.quant-gas↗

arXiv2014

Quantum Mass Acquisition in Spinor Bose-Einstein Condensates

Quantum mass acquisition, in which a massless (quasi)particle becomes massive due to quantum corrections, is predicted to occur in several subfields of physics. However, its experimental observation remains elusive since the emergent energy gap is too small. We show that a spinor Bose-Einstein condensate is an excellent candidate for the observation of such a peculiar phenomenon as the energy gap turns out to be 2 orders of magnitude larger than the zero-point energy. This extraordinarily large energy gap is a consequence of the dynamical instability. The propagation velocity of the resultant massive excitation mode is found to be decreased by the quantum corrections as opposed to phonons.

cond-mat.quant-gas↗

arXiv2013

Fluctuation-induced and symmetry-prohibited metastabilities in spinor Bose-Einstein condensates

Spinor Bose-Einstein condensates provide a unique example in which the Bogoliubov theory fails to describe the metastability associated with first-order quantum phase transitions. This problem is resolved by developing the spinor Beliaev theory which takes account of quantum fluctuations of the condensate. It is these fluctuations that generate terms of higher than the fourth order in the order-parameter field which are needed for the first-order phase transitions. Besides the conventional first-order phase transitions which are accompanied by metastable states, we find a class of first-order phase transitions which are not accompanied by metastable states. The absence of metastability in these phase transitions holds to all orders of approximation since the metastability is prohibited by the symmetry of the Hamiltonian at the phase boundary. Finally, the possibility of macroscopic quantum tunneling from a metastable state to the ground state is discussed.

cond-mat.quant-gas↗

arXiv2012

Beliaev theory of spinor Bose-Einstein condensates

By generalizing the Green's function approach proposed by Beliaev [1, 2], we investigate the effect of quantum depletion on the energy spectra of elementary excitations in an F = 1 spinor Bose-Einstein condensate, in particular, of 87Rb atoms in an external magnetic field. We find that quantum depletion increases the effective mass of magnons in the spin-wave excitations with quadratic dispersion relations. The enhancement factor turns out to be the same for both ferromagnetic and polar phases, and also independent of the magnitude of the external magnetic field. The lifetime of these magnons in a 87Rb spinor BEC is shown to be much longer than that of phonons. We propose an experimental setup to measure the effective mass of these magnons in a spinor Bose gas by exploiting the effect of a nonlinear dispersion relation on the spatial expansion of a wave packet of transverse magnetization. This type of measurement has practical applications, for example, in precision magnetometry.

cond-mat.quant-gas↗