Calculations of Nonlinear Wave-Packet Interferometry Signals in the Pump-Probe Limit as Tests for Vibrational Control over Electronic Excitation Transfer
The preceding paper describes a strategy for externally influencing the course of short-time electronic excitation transfer (EET) in molecular dimers and observing the process by nonlinear wave-packet interferometry (nl-WPI). Within a sample of isotropically oriented dimers having a specified internal geometry, a vibrational mode internal to the acceptor chromophore can be preferentially driven by electronically nonresonant impulsive stimulated Raman (or resonant infrared) excitation with a short polarized control pulse. A subsequent electronically resonant polarized pump then preferentially excites the donor, and EET ensues. Here we test both the control strategy and its spectroscopic investigation-with some sacrifice of amplitude-level detail-by calculating the pump-probe difference signal. That signal is the limiting case of the control-influenced nl-WPI signal in which the two pulses in the pump pulse-pair coincide, as do the two pulses in the probe pulse-pair. We present calculated pump-probe difference signals for (1) a model excitation-transfer complex in which two equal-energy monomers each support one moderately Franck-Condon active intramolecular vibration; (2) a simplified model of the covalent dimer dithia-anthracenophane, representing its EET dynamics following selective impulsive excitation of the weakly Franck-Condon active anthracene vibration at 385 cm-1; and (3) a model complex featuring moderate electronic-vibrational coupling in which the site energy of the acceptor chromophore is lower than that of the donor.
We use a parametric down-conversion source pumped by a short coherence-length continuous-wave (CW) diode laser to perform two-photon interferometry in an intermediate regime between the more familiar Franson-type experiments with a long coherence-length pump laser, and the short pulsed pump "time-bin" experiments pioneered by Gisin's group. The use of a time-bin-like Mach-Zehnder interferometer in the CW pumping beam induces coherence between certain two-photon amplitudes, while the CW nature of the experiment prevents the elimination of remaining incoherent ones. The experimental results high…
We discuss matter wave experiments in a near-field interferometer and focus on dephasing phenomena due to inertial forces. Their presence may result in a significant reduction of the observed interference contrast, even though they do not lead to genuine decoherence. We provide quantitative estimates for the most important effects and demonstrate experimentally the strong influence of acoustic vibrations. Since the effects of inertial forces get increasingly important for the interferometry with more massive particles they have to be identified and compensated in future experiments.
The time-development of photoexcitations in molecular aggregates exhibits specific dynamics of electronic states and vibrational wavefunction. We discuss the dynamical formation of entanglement between electronic and vibrational degrees of freedom in molecular aggregates with theory of electronic energy transfer and the method of vibronic 2D wavepackets [Cina, Kilin, Humble, J. Chem. Phys. 118, 46 (2003)]. The vibronic dynamics is also described by applying Jaynes-Cummings model to the electronic energy transfer [Kilin, Pereverzev, Prezhdo, J. Chem. Phys. 120, 11209 (2004);math-ph/0403023]. Fo…
We investigate the control of electronic energy transfer in molecular dimers through the preparation of specific vibrational coherences prior to electronic excitation, and its observation by nonlinear wave-packet interferometry. Laser-driven coherent nuclear motion can affect the instantaneous resonance between site-excited electronic states and thereby influence short-time electronic excitation transfer (EET). We first illustrate this control mechanism with calculations on a dimer whose constituent monomers undergo harmonic vibrations. We then consider the use of nonlinear wave-packet interfe…
Addressing intramolecular vibrational redistribution in a single molecule through pump and probe surface-enhanced vibrational spectroscopy
Centro de Física de Materiales (CFM-MPC), CSIC-EHU（材料物理中心）；Donostia International Physics Center (DIPC)（多诺西亚国际物理中心）；Department of Electricity and Electronics, FCT-ZTF, UPV-EHU（巴斯克国立大学电气与电子工程系）；Department of Polymers and Advanced Materials, Faculty of Chemistry, The University of the Basque Country, UPV/EHU（巴斯克国立大学化学学院高分子与先进材料系）；IKERBASQUE, Basque Foundation for Science（伊克尔巴斯基克科学基金会）
We review some recent experiments based upon multimode two-photon interference of photon pairs created by spontaneous parametric down-conversion. The new element provided by these experiments is the inclusion of the transverse spatial profiles of the pump, signal and idler fields. We discuss multimode Hong-Ou-Mandel interference, and show that the transverse profile of the pump beam can be manipulated in order to control two-photon interference. We present the basic theory and experimental results as well as several applications to the field of quantum information.
All classical and quantum technologies that encode in and retrieve information from optical fields rely on the ability to selectively manipulate orthogonal field modes of light. Such manipulation can be achieved with high selectivity for polarization modes and transverse-spatial modes. For the time-frequency degree of freedom, this could efficiently be achieved for a limited choice of approximately orthogonal modes, i.e. non-overlapping bins in time or frequency. We recently proposed a method that surmounts the selectivity barrier for sorting arbitrary orthogonal temporal modes [Opt. Lett. {\b…
Fast and efficient state preparation of molecules can be accomplished by optical pumping. Molecular structure that most obviously facilitates cycling involves a strong electronic transition, with favorable vibrational branching (diagonal Franck-Condon factors, aka FCFs) and without any intervening electronic states. Here, we propose important adjustments to those criteria, based on our experience optically pumping SiO$^+$. Specifically, the preference for no intervening electronic states should be revised, and over-reliance on FCFs can miss important features. The intervening electronic state …
Motivated by our observation of fast echo decay and a surprising coherence freeze, we have developed a pump-probe spectroscopy technique for vibrational states of ultracold $^{85}$Rb atoms in an optical lattice to gain information about the memory dynamics of the system. We use pump-probe spectroscopy to monitor the time-dependent changes of frequencies experienced by atoms and to characterize the probability distribution of these frequency trajectories. We show that the inferred distribution, unlike a naive microscopic model of the lattice, correctly predicts the main features of the observed…
We propose and demonstrate a versatile technique to measure the lifetime of the one-phonon Fock state using two-color pump-probe Raman scattering and spectrally-resolved, time-correlated photon counting. Following pulsed laser excitation, the $n=1$ phonon Fock state is probabilistically prepared by projective measurement of a single Stokes photon. The detection of an anti-Stokes photon generated by a second, time-delayed laser pulse probes the phonon population with sub-picosecond time resolution. We observe strongly non-classical Stokes--anti-Stokes correlations, whose decay maps the single p…
This theoretical paper investigates the formation of ground state molecules from ultracold cesium atoms in a two-color scheme. Following previous work on photoassociation with chirped picosecond pulses [Luc-Koenig et al., Phys. Rev. A {\bf 70}, 033414 (2004)], we investigate stabilization by a second (dump) pulse. By appropriately choosing the dump pulse parameters and time delay with respect to the photoassociation pulse, we show that a large number of deeply bound molecules are created in the ground triplet state. We discuss (i) broad-bandwidth dump pulses which maximize the probability to f…
Pumping a nonlinear crystal by an intense radiation results in the optical parametric generation of photons in two modes (the signal and the idler). The quantized electromagnetic field in these modes is described by a continuous-variable quantum state, which is entangled if the pump is a coherent state produced by a laser. The signal and the idler modes remain populated by photons even if the pump becomes incoherent (dephased by a medium, superposed with a thermal state, or produced by an alternative source such as the superluminescent diode). However, the incoherent pump does effect the entan…
Matter-wave interferometry is a highly sensitive tool to measure small perturbations in a quantum system. This property allows the creation of precision sensors for dephasing mechanisms such as mechanical vibrations. They are a challenge for phase measurements under perturbing conditions that cannot be perfectly decoupled from the interferometer, e.g. for mobile interferometric devices or vibrations with a broad frequency range. Here, we demonstrate a method based on second-order correlation theory in combination with Fourier analysis, to use an electron interferometer as a sensor that precise…
A nonlinear interferometry scheme is described theoretically to induce and resolve electron wave- function beating on time scales shorter than the optical cycle of the time-delayed pump and probe pulses. By employing two moderately intense few-cycle laser fields with a stable carrier-envelope phase, a large range of the entire electronic level structure of a quantum system can be retrieved. In contrast to single-photon excitation schemes, the retrieved electronic states include levels that are both dipole- and non-dipole-accessible from the ground electronic state. The results show that strong…
The laser-like coherent emission at 391nm from N$_2$ gas irradiated by strong 800nm pump laser and weak 400nm seed laser is theoretically investigated. Recent experimental observations are well simulated, including temporal profile, optical gain and periodic modulation of the 391nm signal from N$_2^+$. Our calculation sheds light on the long standing controversy on whether population inversion is indispensable for the optical gain. We demonstrate the Ramsey interference fringes of the emission intensity at 391nm formed by additionally injecting another 800nm pump or 400nm seed, which are well …
We study a general problem of the translational/rotational/vibrational/electronic dynamics of a diatomic molecule exposed to an interaction with an arbitrary external electromagnetic field. The theory developed in this paper is relevant to a variety of specific applications. Such as, alignment or orientation of molecules by lasers, trapping of ultracold molecules in optical traps, molecular optics and interferometry, rovibrational spectroscopy of molecules in the presence of intense laser light, or generation of high order harmonics from molecules. Starting from the first quantum mechanical pr…
We investigate the Landau-Zener-Stuckelberg-Majorana interferometry of a superconducting qubit in a semi-infinite transmission line terminated by a mirror. The transmon-type qubit is at the node of the resonant electromagnetic (EM) field, hiding from the EM field. "Mirror, mirror" briefly describes this system, because the qubit acts as another mirror. We modulate the resonant frequency of the qubit by applying a sinusoidal flux pump. We probe the spectroscopy by measuring the reflection coefficient of a weak probe in the system. Remarkable interference patterns emerge in the spectrum, which c…
Molecular polaritons have gained considerable attention due to their potential to control nanoscale molecular processes by harnessing electromagnetic coherence. Although recent experiments with liquid-phase vibrational polaritons have shown great promise for exploiting these effects, significant challenges remain in interpreting their spectroscopic signatures. In this letter, we develop a quantum-mechanical theory of pump-probe spectroscopy for this class of polaritons based on the quantum Langevin equations and the input-output theory. Comparison with recent experimental data shows good agree…
Vibrations, electromagnetic oscillations and temperature drifts are among the main reasons for dephasing in matter-wave interferometry. Sophisticated interferometry experiments, e.g. with ions or heavy molecules, often require integration times of several minutes due to the low source intensity or the high velocity selection. Here we present a scheme to suppress the influence of such dephasing mechanisms - especially in the low-frequency regime - by analyzing temporal and spatial particle correlations available in modern detectors. Such correlations can reveal interference properties that woul…
Entanglement is one of the most intriguing aspects of quantum mechanics and lies at the heart of the ongoing Second Quantum Revolution, where it is a resource that is used in quantum key distribution, quantum computing and quantum teleportation. We report experiments demonstrating the crucial role that entanglement plays in pump-probe experiments involving ionization, which are a hallmark of the novel research field of attosecond science. We demonstrate that the degree of entanglement in a bipartite ion plus photoelectron system, and, as a consequence, the degree of vibrational coherence in th…
Optical dual-pulse pumping actively creates quantum-mechanical superposition of the electronic and phononic states in a bulk solid. We here made transient reflectivity measurements in an n-GaAs using a pair of relative-phase-locked femtosecond pulses and found characteristic interference fringes. This is a result of quantum-path interference peculiar to the dual-pulse excitation as indicated by theoretical calculation. Our observation reveals that the pathway of coherent phonon generation in the n-GaAs is impulsive stimulated Raman scattering at the displaced potential due to the surface-charg…
We demonstrate rotational and vibrational cooling of cesium dimers by optical pumping techniques. We use two laser sources exciting all the populated rovibrational states, except a target state that thus behaves like a dark state where molecules pile up thanks to absorption-spontaneous emission cycles. We are able to accumulate photoassociated cold Cs2 molecules in their absolute ground state (v = 0, J = 0) with up to 40% efficiency. Given its simplicity, the method could be extended to other molecules and molecular beams. It also opens up general perspectives in laser cooling the external deg…
We present a new algorithm for vibrational control in deuterium molecules that is feasible with current experimental technology. A pump mechanism is used to create a coherent superposition of the D2+ vibrations. A short, intense infrared control pulse is applied after a chosen delay time to create selective interferences. A `chessboard' pattern of states can be realized in which a set of even- or odd-numbered vibrational states can be selectively annihilated or enhanced. A technique is proposed for experimental realization and observation of this effect using 5 fs pulses of 790 nm radiation, w…
