We propose the generalized stochastic Liouville equation to investigate the coherent dynamics in single molecule systems coupled to environments which exhibit both nonstationary and non-Markovian features. The generalized stochastic Liouville equation contains a generalized memory kernel associated with both the intrinsic system Hamiltonian and the non-Markovian features of the environmental noise, which returns to the well-known framework established by Kubo in the limit case that the environmental noise is stationary and memoryless. The coherence of the quantum system can be derived by means of the generalized stochastic Liouville equation in two separated averages with no need to consider the statistical characteristics of the environmental noise. We express the exact analytical expressions of the coherence of the single molecule systems induced by the nonstationary and non-Markovian RTN, and the analytical results of the system coherence are in well consistent with that derived by means of some other theoretical approaches.
Based on tensor network realizations of path integrals reducing exponential memory scaling to polynomial efficiency and a Liouville space implementation of a time-discrete quantum memory, we investigate a quantum system simultaneously exposed to two structured reservoirs. For this purpose, we employ a numerically exact quasi-2D tensor network combining both diagonal and off-diagonal system-reservoir interactions with a twofold memory for continuous and discrete retardation effects. As a possible example, we study the non-Markovian dynamical interplay between discrete photonic feedback and stru…
For a certain class of open quantum systems there exists a dynamical symmetry which connects different time-evolved density matrices. We show how to use this symmetry for dynamics in the Liouville space with time-dependent parameters. This allows us to introduce a concept of generalized coherent states (e.g. density matrices) in the Liouville space. Dynamics of this class of density matrices is characterized by robustness with respect to any time-dependent perturbations of the couplings. We study their dynamical context while focusing on common physical situations corresponding to compact and …
Chiral molecules with broken parity symmetries can be modeled as quantum systems with cyclic-transition structures. By using these novel properties, we design two-step laser pulses to distinguish left- and right-handed molecules from the enantiomers. After the applied pulse drivings, one kind chiral molecules are trapped in coherent population trapping state, while the other ones are pumped to the highest states for ionizations. Then, different chiral molecules can be separated.
By using a quantized input light, we theoretically revisit the coherent two-color photo-association process in an atomic Bose-Einstein condensate. Under the single-mode approximations, we show two interesting regimes of the light transmission and the molecular generation. The quantum state transfer from light to molecules is exhibited, without or with the depletion of trapped atoms.
Molecules are ubiquitous in natural phenomena and man-made products, but their use in quantum optical applications has been hampered by incoherent internal vibrations and other phononic interactions with their environment. We have now succeeded in turning an organic molecule into a coherent two-level quantum system by placing it in an optical microcavity. This allows several unprecedented observations such as 99\% extinction of a laser beam by a single molecule, saturation with less than 0.5 photon, and nonclassical generation of few-photon super-bunched light. Furthermore, we demonstrate effi…
The question of whether sunlight induces coherent dynamics in biological systems is under debate. Here we show, on the basis of an exact fully quantum mechanical treatment, that thermal light induces excited-state coherences in matter similar to those induced by a coherent state. We demonstrate the phenomenon on a V-type model system and a two-state Born-Oppenheimer molecular system. Remarkably, wavepacket-like dynamics is induced in the excited molecular potential-energy surface.
We report on the excitation of single molecules via narrow zero-phonon transitions using short laser pulses. By monitoring the Stokes-shifted fluorescence, we studied the excited state population as a function of the delay time, laser intensity, and frequency detuning. A pi-pulse excitation was demonstrated with merely 500 photons, and 5 Rabi cycles were achieved at higher excitation powers. Our findings are in good agreement with theoretical calculations and provide a first step toward coherent manipulation of the electronic states of single molecules with few photons.
The behavior of a single molecule driven simultaneously by a laser and by an electric radio frequency field is investigated using a non-Hermitian Hamiltonian approach. Employing the renormalization group method for differential equations we calculate the average waiting time for the first photon emission event to occur, and determine the conditions for the suppression and enhancement of photon emission. An abrupt transition from localization-like behavior to delocalization behavior is found.
We predict and study the quantum-electrodynamical effect of parametric self-induced excitation of a molecule moving above the dielectric or conducting medium with periodic grating. In this case the radiation reaction force modulates the molecular transition frequency which results in a parametric instability of dipole oscillations even from the level of quantum or thermal fluctuations. The present mechanism of instability of electrically neutral molecules is different from that of the well-known Smith-Purcell and transition radiation in which a moving charge and its oscillating image create an…
A phase controlled wave packet, recently used in experiment of wave packet interferometry of adiatomic molecule, is investigated to obtain mesoscopic superposition structures, useful in quantum metrology. This analysis provides a new way of obtaining sub-Planck scale structures at smaller time scale of revival dynamics. We study a number of situations for delineating the smallest interference structures and their control by tailoring the relative phase between two subsidiary wave packets. We also find the most appropriate state, so far, for high precision parameter estimation in a system of di…
We study two ions confined in a Penning trap. We show that electronically highly excited states exist in which an electron is delocalized among the two ions forming a giant molecule of several micrometer size. At energies close to the top of the Coulomb barrier these molecular states can be regarded as superpositions of Rydberg states of individual ions. We illuminate the possibility to observe coherent charge transfer between the ions. Beyond a critical principal quantum number the electron can coherently tunnel through the Coulomb barrier to an adjacent doubly charged ion. The tunneling occu…
We show that the use of a generalized atom-molecule dark state permits the enhanced coherent creation of triatomic molecules in a repulsive atomic Bose-Einstein condensate, with further enhancement being possible in the case of heteronuclear trimers via the constructive interference between two chemical reaction channels.
We study the quantum dynamics of diatomic molecule driven by a circularly polarized resonant electric field. We look for a quantum effect due to classical chaos appearing due to the overlapping of nonlinear resonances associated to the vibrational and rotational motion. We solve the Schrödinger equation associated with the wave function expanded in term of proper stationary states, $|n>\otimes|lm>$ (vibrational$\otimes$angular momentum states). Looking for quantum-classic correspondence, we consider the Liouville dynamics in the two dimensional phase space defined by the coherent -like state o…
We experimentally characterize the non-equilibrium, room-temperature magnetization dynamics of a spin chain evolving under an effective double-quantum Hamiltonian. We show that the Liouville space operators corresponding to the magnetization and the two-spin correlations evolve 90 degrees out of phase with each other, and drive the transport dynamics. For a nearest-neighbor-coupled N-spin chain, the dynamics are found to be restricted to a Liouville operator space whose dimension scales only as N^2, leading to a slow growth of multi-spin correlations. Even though long-range couplings are prese…
We report on cryogenic coupling of organic molecules to ring microresonators obtained by looping sub-wavelength waveguides (nanoguides). We discuss fabrication and characterization of the chip-based nanophotonic elements which yield resonator finesse in the order of 20 when covered by molecular crystals. Our observed extinction dips from single molecules reach 22%, consistent with the expected Purcell enhancements up to 11 folds. Future efforts will aim at efficient coupling of a handful of molecules via their interaction with a ring microresonator mode, setting the ground for the realization …
The pioneering experiments of linear spectroscopy were performed using flames in the 1800s, but nonlinear optical measurements had to wait until lasers became available in the twentieth century. Because the nonlinear cross section of materials is very small, usually macroscopic bulk samples and pulsed lasers are used. Numerous efforts have explored coherent nonlinear signal generation from individual nanoparticles or small atomic ensembles with millions of atoms. Experiments on a single semiconductor quantum dot have also been reported, albeit with a very small yield. Here, we report on cohere…
The challenge of building a scalable quantum processor requires consolidation of the conflicting requirements of achieving coherent control and preservation of quantum coherence in a large scale quantum system. Moreover, the system should be compatible with miniaturization and integration of quantum circuits. Mesoscopic solid state systems such as superconducting islands and quantum dots feature robust control techniques using local electrical signals and self-evident scaling based on advances in fabrication; however, in general the quantum states of solid state devices tend to decohere rapidl…
Organic dye molecules have been used in great many scientific and technological applications, but their wider use in quantum optics has been hampered by transitions to short-lived vibrational levels, which limit their coherence properties. To remedy this, one can take advantage of optical resonators. Here we present the first results on coherent molecule-resonator coupling, where a single polycyclic aromatic hydrocarbon molecule extinguishes 38\% of the light entering a microcavity at liquid helium temperature. We also demonstrate four-fold improvement of single-molecule stimulated emission co…
Bonding and anti-bonding states of artificial molecules have been realized in experiments by directly coupling two quantum dots. Without a direct coupling between two nearby quantum dots, here we show that a continuous crossover, from symmetric to anti-symmetric molecular state, can be achieved by changing the flux through a double quantum dot Aharonov-Bohm (AB) interferometer. We explicitly present the flux-dependent real-time processes of molecular-state formation. In contrast to the transport current, which has a $2π$ period, the quantum state of the DQD molecule has a $4π$ period in the AB…
We present a quaternion inspired formalism specifically developed to evaluate the intensity of the electrical current that traverses a single molecule connected to two semi-infinite electrodes as the applied external bias is varied. The self-adjustment of the molecular levels is fully described at a density functional ab initio quantum chemical level. Use of a quaternion approach allows for an integrated treatment of both coherent (ballistic) and non-coherent (co-tunneling) contributions to the effective charge transport, where the latter involve the existence of transient charged states of th…
We propose a CNOT gate for quantum computation. The CNOT operation is based on existence of triactive molecules, which in one direction have dipole moment and cause rotation of the polarization plane of linearly polarized light and in perpendicular direction have a magnetic moment. The incoming linearly polarized laser beam is divided into two beams by beam splitter. In one beam a control state is prepared and the other beam is a target. The interaction of polarized states of both beams in a solution containing triactive molecules can be described as interaction of two qubits in CNOT.
We present a new scheme for performing optical spectroscopy on single molecules. A glass capillary with a diameter of 600 nm filled with an organic crystal tightly guides the excitation light and provides a maximum spontaneous emission coupling factor ($β$) of 18% for the dye molecules doped in the organic crystal. Combination of extinction, fluorescence excitation and resonance fluorescence spectroscopy with microscopy provides high-resolution spatio-spectral access to a very large number of single molecules in a linear geometry. We discuss strategies for exploring a range of quantum optical …
The unusual features of quantum mechanics are enabling the development of technologies not possible with classical physics. These devices utilize nonclassical phenomena in the states of atoms, ions, and solid-state media as the basis for many prototypes. Here we investigate molecular states as a distinct alternative. We demonstrate a memory for light based on storing photons in the vibrations of hydrogen molecules. The THz-bandwidth molecular memory is used to store 100-fs pulses for durations up to 1ns, enabling 10,000 operational time bins. The results demonstrate the promise of molecules fo…
Coherent, optically dressed media composed of two-level molecular systems without inversion symmetry are considered as all-optically tunable sources of coherent radiation in the microwave domain. A theoretical model and a numerical toolbox are developed to confirm the main finding: the generation of a low-frequency radiation, and the buildup and propagation dynamics of such low-frequency signals in a medium of polar molecules in a gas phase. The physical mechanism of the signal generation relies on the permanent dipole moment characterizing systems without inversion symmetry. The molecules are…
Arrays of covalently bound organic molecules possess potential for light-harvesting and energy transfer applications due to the strong coherent dipole-dipole coupling between the transition dipole moments of the molecules involved. Here, we show that such molecular systems, based on perylene-molecules, can be considered as arrays of qubits that are amenable for laser-driven quantum coherent control. The perylene monomers exhibit dephasing times longer than four orders of magnitude a typical gating time, thus allowing for the execution of a large number of gate operations on the sub-picosecond …
We investigate a nonlinear localization microscopy method based on Rabi oscillations of single emitters. We demonstrate the fundamental working principle of this new technique using a cryogenic far-field experiment in which subwavelength features smaller than $λ$/10 are obtained. Using Monte Carlo simulations, we show the superior localization accuracy of this method under realistic conditions and a potential for higher acquisition speed or a lower number of required photons as compared to conventional linear schemes. The method can be adapted to other emitters than molecules and allows for th…
We develop an ultrafast frequency-resolved Raman spectroscopy with entangled photons for polyatomic molecules in condensed phases, to probe the electronic and vibrational coherences. Using quantum correlation between the photons, the signal shows the capability of both temporal and spectral resolutions that are not accessible by either classical pulses or the fields without entanglement. We develop a microscopic theory for this Raman spectroscopy, revealing the electronic coherence dynamics which often shows a rapid decay within $\sim$50fs. The heterodyne-detected Raman signal is further devel…
First-order phase transition in atom-molecule quantum degenerate mixtures with coherent three-body recombination
Missouri University of Science and Technology（密苏里科技大学）；Ben-Gurion University of the Negev（内盖夫本古里安大学）；Harvard & Smithsonian（哈佛大学与史密森尼学会）；University of Chicago（芝加哥大学）
Electron and vibrational dynamics of molecules are commonly studied by subjecting them to two interactions with a fast actinic pulse that prepares them in a nonstationary state and after a variable delay period $T$, probing them with a Raman process induced by a combination of a broadband and a narrowband pulse. This technique known as femtosecond stimulated Raman spectroscopy (FSRS) can effectively probe time resolved vibrational resonances. We show how FSRS signals can be modeled and interpreted using the stochastic Liouville equations (SLE) originally developed for NMR lineshapes. The SLE p…
We propose a mechanism to produce a superposition of atomic and molecular states by a train of ultrashort laser pulses combined with weak control fields. By adjusting the repetition rate of the pump pulses and the intensity of the coupling laser, one can suppress a transition while simultaneously enhancing the desired transitions. As an example, various superpositions of vibrational states of the $K_2$ molecule are shown.
We propose a scheme to realize coherent control of spin states of molecule magnet, Ni$_4$. We introduce transverse magnetic fields with special frequencies. When the frequencies of transverse magnetic fields match in some conditions, we obtain dark states in Ni$_4$ molecules. Through adjusting the magnitude of magnetic fields, we can obtain any arbitrary superposition of the two ground spin states of Ni$_4$ molecules.
We demonstrate that it is possible, in principle, to perform a Ramsey-type interference experiment to exhibit a coherent superposition of a single atom and a diatomic molecule. This gedanken experiment, based on the techniques of Aharonov and Susskind [Phys. Rev. 155, 1428 (1967)], explicitly violates the commonly-accepted superselection rule that forbids coherent superpositions of eigenstates of differing atom number. This interference experiment makes use of a Bose-Einstein condensate as a reference frame with which to perform the coherent operations analogous to Ramsey pulses. We also inves…
Multi-electron semiconductor quantum dots have found wide application in qubits, where they enable readout and enhance polarizability. However, coherent control in such dots has typically been restricted to only the lowest two levels, and such control in the strongly interacting regime has not been realized. Here we report quantum control of eight different resonances in a silicon-based quantum dot. We use qubit readout to perform spectroscopy, revealing a dense set of energy levels with characteristic spacing far smaller than the single-particle energy. By comparing with full configuration in…
The long spin coherence times in ambient conditions of color centers in solids, such as nitrogen-vacancy (NV$^{-}$) centers in diamond, make these systems attractive candidates for quantum sensing. Quantum sensing provides remarkable sensitivity at room temperature to very small external perturbations, including magnetic fields, electric fields, and temperature changes. A photoreceptive molecule, such as those involved in vision, changes its charge state or conformation in response to the absorption of a single photon. We show the resulting change in local electric field modifies the propertie…
We demonstrate coherent microwave control of rotational and hyperfine states of trapped, ultracold, and chemically stable $^{23}$Na$^{40}$K molecules. Starting with all molecules in the absolute rovibrational and hyperfine ground state, we study rotational transitions in combined magnetic and electric fields and explain the rich hyperfine structure. Following the transfer of the entire molecular ensemble into a single hyperfine level of the first rotationally excited state, $J{=}1$, we observe collisional lifetimes of more than $3\, \rm s$, comparable to those in the rovibrational ground state…
The purpose of this paper is to articulate a coherent and easy-to-understand way of doing quantum mechanics in any finite-dimensional Liouville space, based on the use of Kronecker product and what we have termed the `bra-flipper' operator. One of the greater strengths of the formalism expatiated on here is the striking similarities it bears with Dirac's bra-ket notation. For the purpose of illustrating how the formalism can be effectively employed, we use it to solve a quantum optical master equation for a two-level quantum system and find its Kraus operator sum representation. The paper is a…
A coherent quantum interface between a neutral atom and a polar molecule
Durham University（杜伦大学）；Universidad de Granada（格拉纳达大学）；Instituto Carlos I de Física Teórica y Computacional, Universidad de Granada（格拉纳达大学卡洛斯一世理论与计算物理研究所）
A coherent control scheme for the population distribution in the vibrational states of nonpolar molecules is proposed. Our theoretical analysis and results of numerical simulations for the interaction of the hydrogen molecular ion in its electronic ground state with an infrared laser pulse reveal a selective two-photon transition between the vibrational states via a coupling with the first excited dissociative state. We demonstrate that for a given temporal intensity profile the population transfer between vibrational states, or a superposition of vibrational states, can be made complete for a…
Optical spectroscopy with broadband femtosecond laser pulses often involves simultaneous excitation of multiple molecular species with close resonance frequencies. Interpreting the collective optical response from molecular mixtures typically requires Fourier analysis of the detected time-resolved signal. We propose an alternative method of separating coherent optical responses from two molecular species with neighboring excitation resonances (here, vibrational modes of oxygen and carbon dioxide). We utilize ro-vibrational coupling as a mechanism of suppressing the strong vibrational response …
Photosynthetic antenna complexes are responsible for absorbing energy from sunlight and transmitting it to remote locations where it can be stored. Recent experiments have found that this process involves long-lived quantum coherence between pigment molecules, called chromophores, which make up these complexes. Expected to decay within 100 fs at room temperature, these coherences were instead found to persist for picosecond time scales, despite having no apparent isolation from the thermal environment of the cell. This paper derives a quantum master equation which describes the coherent evolut…
Extinction spectroscopy is a powerful tool for demonstrating the coupling of a single quantum emitter to a photonic structure. However, it can be challenging in all but the simplest of geometries to deduce an accurate value of the coupling efficiency from the measured spectrum. Here we develop a theoretical framework to deduce the coupling efficiency from the measured transmission and reflection spectra without precise knowledge of the photonic environment. We then consider the case of a waveguide interrupted by a transverse cut in which an emitter is placed. We apply that theory to a silicon …
We study the coherent association of a two-species atomic condensate into a condensate of heteronuclear diatomic molecules, using both a semiclassical treatment and a quantum mechanical approach. The differences and connections between the two approaches are examined. We show that, in this coupled nonlinear atom-molecule system, the population difference between the two atomic species plays a significant role in the ground-state stability properties as well as in coherent population oscillation dynamics.
A new approximate solution to the quantum-classical Liouville equation is derived starting from the formal solution of this equation in forward-backward form. The time evolution of a mixed quantum-classical system described by this equation is obtained in a coherent state basis using the mapping representation, which expresses $N$ quantum degrees of freedom in a 2N-dimensional phase space. The solution yields a simple non-Hamiltonian dynamics in which a set of $N$ coherent state coordinates evolve in forward and backward trajectories while the bath coordinates evolve under the influence of the…
We propose an approach to sensitively probe the chirality of molecules by measuring their coherent optical absorption spectra. It is shown that quantum dynamics of the cyclic three-level chiral molecules driven by appropriately-designed external fields is total-phase dependent. This will result in chirality-dependent absorption spectra for the probe field. As a consequence, these absorption spectra can be utilized to identify molecular chirality and determinate enantiomer excess. The feasibility of the proposal with chiral molecules confined in hollow-core photonic crystal fiber (HC-PCF) is al…
Ultracold molecules have experienced increasing attention in recent years. Compared to ultracold atoms, they possess several unique properties that make them perfect candidates for the implementation of new quantum-technological applications in several fields, from quantum simulation to quantum sensing and metrology. In particular, ultracold molecules of two-electron atoms (such as strontium or ytterbium) also inherit the peculiar properties of these atomic species, above all the possibility to access metastable electronic states via direct excitation on optical clock transitions with ultimate…
The application of a matrix-based reconstruction protocol for obtaining Molecular Frame (MF) photoelectron angular distributions (MFPADs) from laboratory frame (LF) measurements (LFPADs) is explored. Similarly to other recent works on the topic of MF reconstruction, this protocol makes use of time-resolved LF measurements, in which a rotational wavepacket is prepared and probed via photoionization, followed by a numerical reconstruction routine; however, in contrast to other methodologies, the protocol developed herein does not require determination of photoionization matrix elements, and cons…
High harmonic light sources make it possible to access attosecond time-scales, thus opening up the prospect of manipulating electronic wave packets for steering molecular dynamics. However, two decades after the birth of attosecond physics, the concept of attosecond chemistry has not yet been realized. This is because excitation and manipulation of molecular orbitals requires precisely controlled attosecond waveforms in the deep ultraviolet, which have not yet been synthesized. Here, we present a novel approach using attosecond vacuum ultraviolet pulse-trains to coherently excite and control t…
We present expressions demonstrating that collisional decoherence of ultracold atoms or molecules in a coherent superposition of non-degenerate quantum states is suppressed when both the real and imaginary parts of the scattering lengths for the states in the coherent superposition are equal. We show that the rate of collisional decoherence can be enhanced or suppressed by varying an external magnetic field near a Feshbach resonance. For some resonances, the suppression is very dramatic. We propose a method for measuring the scattering length of ultracold particles in excited quantum states ex…
We study the possibility to use interaction between a polar molecule in the ground electronic and vibrational state and a Rydberg atom to construct two-qubit gates between molecular qubits and to coherently control molecular states. A polar molecule within the electron orbit in a Rydberg atom can either shift the Rydberg state, or form Rydberg molecule. Both the atomic shift and the Rydberg molecule states depend on the initial internal state of the polar molecule, resulting in molecular state dependent van der Waals or dipole-dipole interaction between Rydberg atoms. Rydberg atoms mediated in…
A pair of coherent femtosecond pulse excitations applied to a molecule with strong electron-phonon coupling creates a coherent superposition of a low momentum and a high momentum wavepacket in the vibrational states of both the excited state and the ground state of the coherent transition. As the excited state is accelerated further, interference between the high momentum ground state contribution and the low momentum excited state contribution causes a photon echo. This photon echo is a direct consequence of quantum interference between separate vibrational trajectories and can therefore prov…
The success of the emerging field of solid-state optical quantum information processing (QIP) critically depends on the access to resonant optical materials. Rare-earth ions (REIs) are suitable candidates for QIP protocols due to their extraordinary photo-physical and magnetic quantum properties such as long optical and spin coherence lifetimes ($T_2$). However, molecules incorporating REIs, despite having advantageous properties such as atomically exact quantum tunability, inherent scalability, and large portability, have not yet been studied for QIP applications. As a first testimony of the …
