Signature of Molecular Orbital Symmetry in High-Order Harmonic Generation by Bichromatic Circularly Polarized Laser Pulses.

Molecular orbital symmetry is shown to be an important factor in determining orders and helicities (polarizations) of high-order harmonic generation (HHG) by intense femtosecond counter-rotating bichromatic circularly polarized laser pulses. Numerical solutions of time-dependent Schrödinger equations (TDSE) for the one-electron molecular ions H2+ and H32+ for different initial electronic states show that harmonic orders and helicities are dependent on orbital symmetries and of the net incident pulse electric field. The numerical results and properties of the harmonics are described by dynamical symmetry theory and time profile analysis of the high-order harmonics, thus confirming that orbital and laser pulse symmetry dependence are generic in HHG of molecules.

Lifetime-Engineered Carbon Nanodots for Time Division Duplexing.

Optical multiplexing attracts considerable attention in the field of information encryption, optical probe, and time-resolved bioimaging. However, the optical multiplexing based on rare-earth nanoparticles suffers from heavy metal elements and relatively short lifetimes; sophisticated facilities are thus needed. Herein, time division duplexing based on eco-friendly carbon nanodots (CNDs) with manipulative luminescence lifetimes is demonstrated. In a single green color emission channel, the luminescence lifetimes of the CNDs can be manipulated from nanosecond level to second level by introducing water, while the lifetime of the CNDs confined by a silica shell stays. Time division duplexing based on the CNDs and CNDs@silica with distinct lifetimes is realized and spatio-temporal overlapping information is thus resolved. High-level information encryption using the time division duplexing technology is realized. This work may promise the potential applications of CNDs in multi-lifetime channels biological imaging, high-density information storage, and anti-counterfeiting.

Attosecond all-optical control and visualization of quantum interference between degenerate magnetic states by circularly polarized pulses.

Controlling coherence and interference of quantum states is one of the central goals in quantum science. Different from energetically discrete quantum states, however, it remains a demanding task to visualize coherent properties of degenerate states (e.g., magnetic sublevels). It becomes further inaccessible in the absence of an external perturbation (e.g., Zeeman effect). Here, we present a theoretical analysis of all-optical control of degenerate magnetic states in the molecular hydrogen ion, $ {\rm H}_2^ + $H2+, by using two time-delayed co- and counterrotating circularly polarized attosecond extreme-ultraviolet (XUV) pulses. We perform accurate simulations to examine this model by solving the three-dimensional time-dependent Schrödinger equation. A counterintuitive phenomenon of quantum interference between degenerate magnetic sublevels appears in the time-dependent electronic probability density, which is observable by using x-ray-induced transient angular and energy-resolved photoelectron spectra. This work provides an insight into quantum interference of electron dynamics inside molecules at the quantum degeneracy level.

Ultrafast X-ray photoelectron diffraction in triatomic molecules by circularly polarized attosecond light pulses.

We theoretically study ultrafast photoelectron diffraction in triatomic molecules with cyclic geometry by ultrafast circular soft X-ray attosecond pulses. Molecular frame photoelectron distributions show complex diffraction patterns, arising from molecular multiple center interference and circular charge migration. It is found that photoelectron diffraction patterns depend on the initial electronic state, encoding the information of molecular orbital symmetries. In a resonant coherent electron excitation process, time-resolved photoelectron diffraction patterns enables us to reconstruct the charge migration with highly spatiotemporal resolutions. We simulate and analyze the results from ab initio calculations of the single electron triangular hydrogen molecular ion H32+ which is used as a benchmark molecular system in combination with an ultrafast multi-center and multi-state photoionization model. This approach presents a general scheme which can be applied to explore circular charge migration from electron orbits and attosecond coherent electron dynamics in polyatomic systems by circular ultrafast laser pulses.

Efficient Red/Near-Infrared-Emissive Carbon Nanodots with Multiphoton Excited Upconversion Fluorescence.

Red/near-infrared (NIR) emissive carbon nanodots (CNDs) with photoluminescence (PL) quantum yield (QY) of 57% are prepared via an in situ solvent-free carbonization strategy for the first time. 1-Photon and 2-photon cellular imaging is demonstrated by using the CNDs as red/NIR fluorescence agent due to the high PL QY and low biotoxicity. Further study shows that the red/NIR CNDs exhibit multiphoton excited (MPE) upconversion fluorescence under excitation of 800-2000 nm, which involves three NIR windows (NIR-I, 650-950 nm; NIR-II, 1100-1350; NIR-III, 1600-1870 nm). 2-Photon, 3-photon, and 4-photon excited fluorescence of the CNDs under excitation of different wavelengths is achieved. This study develops an in situ solvent-free carbonization method for efficient red/NIR emissive CNDs with MPE upconversion fluorescence, which may push forward the application of the CNDs in bioimaging.

Ultrafast X-ray Photoelectron Imaging of Attosecond Electron Dynamics in Molecular Coherent Excitation.

Ultrafast photoelectron imaging allows to measure information about coherent electron dynamic processes in materials or chemical compounds on femtosecond to attosecond time scales. We show that molecular time-resolved photoelectron diffraction produced by a time-delayed soft X-ray attosecond pulse can be used to monitor the ultrafast coherent excitation induced by a resonant UV pump pulse with variable carrier-envelope phases. Asymmetric diffraction angular patterns illustrate coherent electron dynamics of charge migration with spatiotemporal resolution on the attosecond and ångström scale. This allows the temporal reconstruction of phases and amplitudes of electronic states and geometry of molecules as a function of time delay of the probe pulse and carrier-envelope phases of the pump pulse. Results are obtained from solutions of time-dependent Schrödinger equations of the hydrogen molecular ion, and analyzed by ultrafast photoelectron diffraction models for coherent superposition of electronic states. The present demonstration provides a guiding principle for monitoring ultrafast spatiotemporal coherent electron dynamics and imaging molecular electronic structure in complex systems by ultrafast pump-probe experiments and their dependence on carrier-envelope phases and time delays.

Time-Resolved Photoelectron Imaging of Molecular Coherent Excitation and Charge Migration by Ultrashort Laser Pulses.

Charge migration is a fundamental and important process in the photochemistry of molecules and has been explored by time-resolved photoelectron angular distributions. A scheme based on UV pump and polarized soft X-ray probe techniques shows that photoelectron diffraction effects enable us to reconstruct electronic coherences encoding the information of the charge migration with extreme time resolutions. We discuss how probe pulse helicity influences the probing photoelectron spectra in the presence of molecular nonspherical Coulomb potentials. This phenomenon is analyzed theoretically and simulated via ab initio calculations for the molecular hydrogen ion, offering a reliable approach for measurements of charge migration and for the exploration of molecular structure in attosecond science.

Exploring coherent electron excitation and migration dynamics by electron diffraction with ultrashort X-ray pulses.

Exploring ultrafast charge migration is of great importance in biological and chemical reactions. We present a scheme to monitor attosecond charge migration in molecules by electron diffraction with spatial and temporal resolutions from ab initio numerical simulations. An ultraviolet pulse creates a coherent superposition of electronic states, after which a time-delayed attosecond X-ray pulse is used to ionize the molecule. It is found that diffraction patterns in the X-ray photoelectron spectra show an asymmetric structure, which is dependent on the time delay between the pump-probe pulses, encoding the information of molecular orbital symmetry and chemical bonding. We describe these phenomena by developing an electronic time-dependent ultrafast molecular photoionization model of a coherent superposition state. The periodical distortion of electron diffraction patterns illustrates the evolution of the electronic coherence, providing a tool for attosecond imaging of ultrafast molecular reaction processes.

Attosecond Dynamics of Molecular Electronic Ring Currents.

Ultrafast charge migration is of fundamental importance to photoinduced chemical reactions. However, exploring such a quantum dynamical process requires demanding spatial and temporal resolutions. We show how electronic coherence dynamics induced in molecules by a circularly polarized UV pulse can be tracked by using a time-delayed circularly polarized attosecond X-ray pulse. The X-ray probe spectra retrieve an image at different time delays, encoding instantaneous pump-induced circular charge migration information on an attosecond time scale. A time-dependent ultrafast electronic coherence associated with the periodical circular ring currents shows a strong dependence on the helicity of the UV pulse, which may provide a direct approach to access and control the electronic quantum coherence dynamics in photophysical and photochemical reactions in real time.

Identifying Strong-Field Effects in Indirect Photofragmentation Reactions.

Exploring molecular breakup processes induced by light-matter interactions has both fundamental and practical implications. However, it remains a challenge to elucidate the underlying reaction mechanism in the strong field regime, where the potentials of the reactant are modified dramatically. Here we perform a theoretical analysis combined with a time-dependent wavepacket calculation to show how a strong ultrafast laser field affects the photofragment products. As an example, we examine the photochemical reaction of breaking up the molecule NaI into the neutral atoms Na and I, which due to inherent nonadiabatic couplings are indirectly formed in a stepwise fashion via the reaction intermediate NaI*. By analyzing the angular dependencies of fragment distributions, we are able to identify the reaction intermediate NaI* from the weak to the strong field-induced nonadiabatic regimes. Furthermore, the energy levels of NaI* can be extracted from the quantum interference patterns of the transient photofragment momentum distribution.

Monitoring coherent electron wave packet excitation dynamics by two-color attosecond laser pulses.

We propose a method to monitor coherent electron wave packet (CEWP) excitation dynamics with two-color attosecond laser pulses. Simulations are performed on aligned H2+ by numerically solving the three-dimensional time-dependent Schrödinger equation with combinations of a resonant linearly polarized λl= 100/70 nm pump pulse and a circularly polarized λc=5 nm attosecond probe pulse. It is found that time dependent diffraction patterns in molecular frame photoelectron angular distributions (MFPADs) produced by the circular probe pulse exhibit sensitivity to the molecular alignments and time-dependent geometry of the CEWPs during and after the coherent excitation between the ground and excited states induced by the linear pump pulse. The time dependent MFPADs are described by an ultrafast diffraction model for the ionization of the bound CEWPs.

Molecular photoelectron angular distribution rotations in multi-photon resonant ionization of H2(+) by circularly polarized ultraviolet laser pulses.

We study effects of pulse durations on molecular photoelectron angular distributions (MPADs) in ultrafast circular polarization ultraviolet resonant ionization processes. Simulations performed on aligned H2 (+) by numerically solving time dependent Schrödinger equations show rotations of MPADs with respect to the molecular symmetry axes. It is found that in multi-photon resonant ionization processes, rotation angles are sensitive to pulse durations, which we attribute to the coherent resonant excitation between the ground state and the intermediate excited electronic state induced by Rabi oscillations. Multi-photon nonresonant and single photon ionization processes are simulated and compared which exhibit a constant rotation angle. An asymmetry parameter is introduced to describe the pulse duration sensitivity by perturbation theory models. Influence of pulse frequency detunings on MPADs is also investigated where oscillations of rotations are absent at long pulse durations due to nonresonance excitation.

Molecular alignment dependent electron interference in attosecond ultraviolet photoionization.

We present molecular photoionization processes by intense attosecond ultraviolet laser pulses from numerical solutions of time-dependent Schrödinger equations. Simulations preformed on a single electron diatomic [Formula: see text] show minima in molecular photoelectron energy spectra resulting from two center interference effects which depend strongly on molecular alignment. We attribute such sensitivity to the spatial orientation asymmetry of the photoionization process from the two nuclei. A similar influence on photoelectron kinetic energies is also presented.

Electron interference in molecular photoionization by attosecond laser pulses.

Molecular photoionization by intense attosecond linearly and circularly polarized X-ray laser pulses is investigated from numerical solutions of time-dependent Schrödinger equations for the one-electron systems H2(+) and H3(++). Both momentum stripes and rings in photoelectron angular distributions are observed. The first with momentum intervals Δp(s)=2 π/R, where R is the molecular internuclear distance, results from interference of the coherent continuum scattering electron wave packets, which is shown to be insensitive to the laser polarization and wavelength. Diffraction of the directly ionized electrons leads to the momentum rings defined by the angle theta(p(r)R=cos(-1)(2nπ)/p(r)R between the electron momentum p(r) and the molecular internuclear R axis. These patterns are well described by multi-center interference models. Such complex patterns allow us to probe intermolecular structures.

Rotations of molecular photoelectron angular distributions with intense ultrashort circularly polarized attosecond laser pulses.

Molecular photoelectron angular distributions (MPADs) by intense (I0 ≥ 10(14) W/cm(2)) circularly polarized ultrashort, few cycle (attosecond) ultraviolet laser pulses are presented from numerical solutions of time dependent Schrödinger equations. For the aligned molecular ion H2(+), the MPADs exhibit rotations with respect to the polarization and molecular symmetry axes which are determined by the symmetry of the initial electronics states. It is also found that the rotation angle of MPADs is insensitive to the pulse intensity. We attribute these effects to the asymmetry between the parallel and perpendicular (to the molecular axis) polarization photoionization. Influence of the molecular alignment and ionizing pulse ellipticity on the rotation of MPADs is also shown to allow control of the nonsymmetric ionization.

Single circularly polarized attosecond pulse generation by intense few cycle elliptically polarized laser pulses and terahertz fields from molecular media.

We present a method for producing a single circularly polarized attosecond pulse by an intense few cycle elliptically polarized laser pulse combined with a terahertz field from numerical solutions of the time-dependent Schrödinger equation for the molecular ion H2(+). It is found that in the presence of a 62.5 THz (λ=4800 nm) field at an intensity of ∼10(14) W/cm2, a single circularly polarized 114 as pulse can be generated by an elliptical polarized laser pulse at a wavelength of 400 nm with an ellipticity of ϵ=0.59. The efficiency of circular polarization attosecond pulse generation is interpreted based on a classical model of single electron recollision with the parent ion.

Field-free molecular orientation with terahertz few-cycle pulses.

We demonstrate theoretically an efficient field-free orientation in LiH and LiCl driven by available terahertz few-cycle pulses (TFCPs). Exact results by numerically solving the time-dependent Schrodinger equation including the vibrational and rotational degrees of freedom are compared to the rigid-rotor approximation (RRA) as well as to the impulsive approximation (IA), and the effect of rotational-vibrational coupling on the both RRA and IA is examined in detail. We find that the current available TFCPs may overcome the technical limitation of terahertz half-cycle pulse for enhancing the field-free molecular orientation.

Determination of the phase of terahertz few-cycle laser pulses.

We propose an approach to determine the carrier-envelope phase (CEP) of a terahertz few-cycle pulse by observing the field-free molecular orientation. We find that the degree of orientation sensitively depends on the CEP, providing a new route for measuring the CEP without phase ambiguity. By taking advantage of the field-free molecular orientation, an important effect of the CEP drift caused by the dephasing of the generating medium on the accurate measurement of the CEP value is eliminated.

Control of photodissociation and photoionization of the NaI molecule by dynamic Stark effect.

The diabatic photodissociation and photoionization processes of the NaI molecule are studied theoretically using the quantum wave packet method. A pump laser pulse is used to prepare a dissociation wave packet that propagates through both the ionic channel (NaI-->Na(+)+I(-)) and the covalent channel (NaI-->Na+I). A Stark pulse is used to control the diabatic dissociation dynamics and a probe pulse is employed to ionize the products from the two channels. Based on the first order nonresonant nonperturbative dynamic Stark effect, the dissociation probabilities and the branching ratio of the products from the two channels can be controlled. Moreover the final photoelectron kinetic energy distribution can also be affected by the Stark pulse. The influences of the delay time, intensity, frequency, and carrier-envelope phase of the Stark pulse on the dissociation and ionization dynamics of the NaI molecule are discussed in detail.

Steering dissociation of Br2 molecules with two femtosecond pulses via wave packet interference.

The dissociation dynamics of Br2 molecules induced by two femtosecond pump pulses are studied based on the calculation of time-dependent quantum wave packet. Perpendicular transition from X 1Sigma g+ to A 3Pi 1u+ and 1Pi 1u+ and parallel transition from X 1Sigma g+ to B 3Pi 0u+, involving two product channels Br (2P3/2)+Br (2P3/2) and Br (2P3/2)+Br* (2P1/2), respectively, are taken into account. Two pump pulses create dissociating wave packets interfering with each other. By varying laser parameters, the interference of dissociating wave packets can be controlled, and the dissociation probabilities of Br2 molecules on the three excited states can be changed to different degrees. The branching ratio of Br*/(Br+Br*) is calculated as a function of pulse delay time and phase difference.