Molecules In Strong Laser Fields Research Articles

Controlling quantum effects in enhanced strong-field ionisation with machine-learning techniques

We study non-classical pathways and quantum interference in enhanced ionisation of diatomic molecules in strong laser fields using machine learning techniques. Quantum interference provides a ‘bridge’, which facilitates intramolecular population transfer. Its frequency is higher than that of the field, intrinsic to the system and depends on several factors, for instance the state of the initial wavepacket or the internuclear separation. Using dimensionality reduction techniques, namely t-distributed stochastic neighbour embedding and principal component analysis, we investigate the effect of multiple parameters at once and find optimal conditions for enhanced ionisation in static fields, and controlled ionisation release for two-colour driving fields. This controlled ionisation manifests itself as a step-like behaviour in the time-dependent autocorrelation function. We explain the features encountered with phase-space arguments, and also establish a hierarchy of parameters for controlling ionisation via phase-space Wigner quasiprobability flows, such as specific coherent superpositions of states, electron localisation and internuclear-distance ranges.

Real-time calibration of nuclear velocities in the dissociation of heteronuclear molecules in strong laser fields

We design a strategy for the real-time calibration of nuclear velocities in ultrafast molecular reactions in strong laser fields by simulating the four-dimensional time-dependent Schr\"odinger equation. Taking $\mathrm{H}{\mathrm{D}}^{+}$ as the prototype, an attosecond pump pulse initiates the molecular dissociation, and the other time-delayed attosecond probe pulse, polarized in the plane perpendicular to the molecular axis, ionizes the dissociating $\mathrm{H}{\mathrm{D}}^{+}$. During the dissociation, two nuclei with different masses acquire different velocities, which imprint on the photoelectron kicked off by the probe pulse. The expected photoelectron momentum along the molecular axis can be used to precisely calibrate instantaneous nuclear velocities at ionization. This strategy works widely in general heteronuclear molecules and paves the way for making high-definition molecular movies.

Transient Valence Charge Localization in Strong-Field Dissociative Ionization of HCl Molecules.

Probing transient charge localization in the innershell orbital of atoms and molecules has been made possible by the recent progress of advanced light sources. Here, we demonstrate that the ultrafast electron tunneling ionization by an intense femtosecond laser pulse could induce an asymmetric transient charge localization in the valence shell of the HCl molecule during the dissociative ionization process. The transient charge localization is encoded in the laser impulse acquired by the outgoing ionic fragments, and the asymmetry is revealed by carefully examining the electron tunneling-site distinguished momentum angular distribution of the ejected H^{+} fragments. Our work proposes a way to visualize the transient valence charge motion and will stimulate further investigations of the tunneling-site-sensitive ultrafast dynamics of molecules in strong laser fields.

High ellipticity of harmonics from molecules in strong laser fields of small ellipticity

We study high-order harmonic generation (HHG) from aligned molecules in strong elliptically polarized laser fields numerically and analytically. Our simulations show that the spectra and polarization of HHG depend strongly on the molecular alignment and the laser ellipticity. In particular, for small laser ellipticity, large ellipticity of harmonics with high intensity is observed for parallel alignment, with forming a striking ellipticity hump around the threshold. We show that the interplay of the molecular structure and two-dimensional electron motion plays an important role here. This phenomenon can be used to generate bright elliptically-polarized EUV pulses.

Strong-field ionization of water: Nuclear dynamics revealed by varying the pulse duration

Polyatomic molecules in strong laser fields can undergo substantial nuclear motion within tens of femtoseconds. Ion imaging methods based on dissociation or Coulomb explosion therefore have difficulty faithfully recording the geometry dependence of the field ionization that initiates the dissociation process. Here we compare the strong-field double ionization and subsequent dissociation of water (both H$_2$O and D$_2$O) in 10-fs and 40-fs 800-nm laser pulses. We find that 10-fs pulses turn off before substantial internuclear motion occurs, whereas rapid internuclear motion can take place during the double ionization process for 40-fs pulses. The short-pulse measurements are consistent with a simple tunnel ionization picture, whose predictions help interpret the motion observed in the long-pulse measurements.

Quantitative theory for electron-nuclear energy sharing in molecular ionization

The dynamics of molecules in strong laser fields is much more complicated than that of atoms. For example, molecules can break up through dissociative single ionization, in which the electronic dynamics and nuclear dynamics are strongly correlated with each other. In this work we develop a quantitative theory based on the strong-field approximation to describe the dissociative single ionization of a hydrogen molecule, which allows us to schematically investigate the electron-nuclear energy sharing in the dissociative and the nondissociative single ionization of ${\text{H}}_{2}$ induced by intense laser pulses. Under different parameters of the laser pulse, we are able to discuss various types of dynamics in the framework of energy sharing, such as bond softening, dynamical quenching, vibrational trapping, and inverse bond hardening. In particular, we find drastic differences in the electron-nuclear energy sharing for UV and IR pulses. The current theoretical framework can potentially be extended to examine other strong-field phenomena in which the dynamics of different particles are correlated.

Spiral nuclear momentum distribution for the dissociation of H2+ in a circularly polarized laser pulse

The dissociation of ${\mathrm{H}}_{2}{}^{+}$ in a circularly polarized laser pulse is numerically studied by simulating the time-dependent Schr\odinger equation. After absorbing one or three photons, the nuclear wave packets carrying the angular momenta $\ensuremath{\hbar}$ and $3\ensuremath{\hbar}$ dissociate along the $2p{\ensuremath{\sigma}}_{u}$ state. Due to the broad initial kinetic-energy distribution of the superimposed nuclear vibrational states, the one-photon and three-photon dissociation pathways may end with the same kinetic energy. These coexisting dissociation pathways with same parities but different orbital angular momenta interfere with each other, resulting in the spiral nuclear momentum distribution in the laser polarization plane. The interference structure in the nuclear momentum distribution offers another freedom to identify the dissociation pathways of molecules in strong laser fields.

Alignment-dependent ionization of nonlinear triatomic molecules in strong laser fields

The alignment- and channel-resolved ionization of the triatomic nonlinear molecules SO2 and H2O in strong fields has been studied using the strong-field approximation theory. When the instantaneous electric field points from O to S in SO2 or from H to O in H2O, the ionization rate is much larger than in the opposite case. The antibonding nature and destructive interference of the electron wave packets with opposite phases lead to distinct ionization suppression on the highest occupied molecular orbital (HOMO) of H2O and HOMO-1 of SO2. By controlling the relative intensity of the two-color 800 and 400 nm laser fields, the orientation-dependent ionization rate can be manipulated, and the electrons emitted from the different molecular orbitals can be disentangled in space. The orientation- and molecular-orbital-resolved ionization can be used to retrieve the complex structure of molecules to image the molecular orbitals HOMO, HOMO-1, and HOMO-2 as well as to steer the photoelectron emission of the laser-driven nonlinear molecules.

H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields

Roaming mechanisms, involving the brief generation of a neutral atom or molecule that stays in the vicinity before reacting with the remaining atoms of the precursor, are providing valuable insights into previously unexplained chemical reactions. Here, the mechanistic details and femtosecond time-resolved dynamics of H3+ formation from a series of alcohols with varying primary carbon chain lengths are obtained through a combination of strong-field laser excitation studies and ab initio molecular dynamics calculations. For small alcohols, four distinct pathways involving hydrogen migration and H2 roaming prior to H3+ formation are uncovered. Despite the increased number of hydrogens and possible combinations leading to H3+ formation, the yield decreases as the carbon chain length increases. The fundamental mechanistic findings presented here explore the formation of H3+, the most important ion in interstellar chemistry, through H2 roaming occurring in ionic species.

Identifying the Multielectron Effect on Chemical Bond Rearrangement of CH3Cl Molecules in Strong Laser Fields

Strong field double ionization that triggers the chemical bond rearrangement of CH3Cl is investigated by impulsive control of the alignment of molecules. The alignment and laser intensity dependent H2+ and H3+ yields in linearly polarized femtosecond laser have been measured, and the obtained data show that the maximum signal of H2+ appears at the laser polarization parallel to the C-Cl axis of molecules and H3+ species are more likely to eject at the laser polarization parallel to the C-Cl axis at low laser intensity while the H3+ signal peaks at laser polarization perpendicular to the C-Cl axis at high laser intensity. The measurements indicate that electrons from HOMO - 1 and HOMO - 2 orbitals have been ionized for the generation of bond rearrangement at different laser intensity. Our results demonstrate the importance of multielectron effects and also provide an effective control method in the process of chemical bond rearrangement of the molecules in strong laser fields.

Disentangling Strong-Field Multielectron Dynamics with Angular Streaking.

The study into the interaction between a strong laser field and atoms/molecules has led to significant advances in developing spectroscopic tools in the attosecond time-domain and methods for controlling chemical reactions. There has been great interest in understanding the complex electronic and nuclear dynamics of molecules in strong laser fields. However, it is still a formidable challenge to fully model such dynamics. Conventional experimental tools such as photoelectron spectroscopy encounter difficulties in revealing the involved states because the electron spectra are largely dictated by the property of the laser field. Here, with strong field angular streaking technique, we measure the angle-dependent ionization yields that directly reflect the symmetry of the ionizing orbitals of methyl iodide and thus reveal the ionization/dissociation dynamics. Moreover, kinematically complete measurements of momentum vectors of all fragments in dissociative double ionization processes allow access to electron-momentum correlations that reveal correlated multielectron dynamics.

Tunnel ionization of atoms and molecules: How accurate are the weak-field asymptotic formulas?

Weak-field asymptotic formulas for the tunnel ionization rate of atoms and molecules in strong laser fields are often used for the analysis of strong field recollision experiments. We investigate their accuracy and domain of validity for different model systems by confronting them to exact numerical results, obtained by solving the time dependent Schrödinger equation. We find that corrections that take the dc-Stark shift into account are a simple and efficient way to improve the formula. Furthermore, analyzing the different approximations used, we show that error compensation plays a crucial role in the fair agreement between exact and analytical results.

Adiabatic perturbation theory for atoms and molecules in the low-frequency regime.

There is an increasing interest in the photoinduced dynamics in the low frequency, ω, regime. The multiphoton absorptions by molecules in strong laser fields depend on the polarization of the laser and on the molecular structure. The unique properties of the interaction of atoms and molecules with lasers in the low-frequency regime imply new concepts and directions in strong-field light-matter interactions. Here we represent a perturbational approach for the calculations of the quasi-energy spectrum in the low-frequency regime, which avoids the construction of the Floquet operator with extremely large number of Floquet channels. The zero-order Hamiltonian in our perturbational approach is the adiabatic Hamiltonian where the atoms/molecules are exposed to a dc electric field rather than to ac-field. This is in the spirit of the first step in the Corkum three-step model. The second-order perturbation correction terms are obtained when iℏω∂∂τ serves as a perturbation and τ is a dimensionless variable. The second-order adiabatic perturbation scheme is found to be an excellent approach for calculating the ac-field Floquet solutions in our test case studies of a simple one-dimensional time-periodic model Hamiltonian. It is straightforward to implement the perturbation approach presented here for calculating atomic and molecular energy shifts (positions) due to the interaction with low-frequency ac-fields using high-level electronic structure methods. This is enabled since standard quantum chemistry packages allow the calculations of atomic and molecular energy shifts due to the interaction with dc-fields. In addition to the shift of the energy positions, the energy widths (inverse lifetimes) can be obtained at the same level of theory. These energy shifts are functions of the laser parameters (low frequency, intensity, and polarization).

Contribution of resonance excitation on ionization of OCS molecules in strong laser fields

Photoelectron images from single ionization of OCS molecules are measured at 800 nm or 400 nm linearly polarized laser pulses (∼50 fs) using velocity-map imaging techniques. The resonant ionization of the molecules has been studied by tracing the electron energy shift in the photoelectron energy spectra at different laser intensities, and the contributions of three excited states at certain laser intensities and wavelengths are identified. During the ionization of OCS molecules, two excited states (1Δ and 1∏) are shifted into resonance at different 800 nm laser intensities, and the Rydberg state 4pσ ∏ is involved in the resonance for a 400 nm laser. The demonstration of resonant excitation contribution experimentally will help further the understanding of OCS ionization in strong laser fields.

Ionization dynamics of polar molecules in strong elliptical laser fields

We study ionization dynamics of oriented polar molecules in strong elliptically polarized laser fields. The calculated photoelectron momentum distributions show an irregular half-ring structure from which we track the electron motion and identify two different ionization channels, i.e., the ground-state one and the excited-state one. We show that the excited-state channel is usually temporally delayed by a few hundred attoseconds in comparison with the ground-state one. This dynamical delay is mapped in the momentum distribution, resulting in the irregular half-ring structure. The characteristics of this structure provide potential observables for studying excited-state effects in ionization of polar molecules in strong laser fields.

Mechanisms and time-resolved dynamics for trihydrogen cation (H3+) formation from organic molecules in strong laser fields

Strong-field laser-matter interactions often lead to exotic chemical reactions. Trihydrogen cation formation from organic molecules is one such case that requires multiple bonds to break and form. We present evidence for the existence of two different reaction pathways for H3+ formation from organic molecules irradiated by a strong-field laser. Assignment of the two pathways was accomplished through analysis of femtosecond time-resolved strong-field ionization and photoion-photoion coincidence measurements carried out on methanol isotopomers, ethylene glycol, and acetone. Ab initio molecular dynamics simulations suggest the formation occurs via two steps: the initial formation of a neutral hydrogen molecule, followed by the abstraction of a proton from the remaining CHOH2+ fragment by the roaming H2 molecule. This reaction has similarities to the H2 + H2+ mechanism leading to formation of H3+ in the universe. These exotic chemical reaction mechanisms, involving roaming H2 molecules, are found to occur in the ~100 fs timescale. Roaming molecule reactions may help to explain unlikely chemical processes, involving dissociation and formation of multiple chemical bonds, occurring under strong laser fields.

Contribution of resonance excitation on ionization of OCS molecules in strong laser field

SynopsisThe resonant enhanced multiphoton ionization (REMPI) of OCS molecules has been studied by tracing the electron energy shift with the laser intensity dependent photoelectron energy spectra. We find that two excited states (1Δ and 1Π) have been involved in the ionization of OCS at 800 nm and the REMPI through a certain excited state can be selectively controlled by varying the laser intensity. Furthermore, the REMPI of OCS through 4sσ Rydberg states at 400 nm laser fields has also been identified by angular distribution of electrons.

Ion-ion coincidence imaging at high event rate using an in-vacuum pixel detector.

A new ion-ion coincidence imaging spectrometer based on a pixelated complementary metal-oxide-semiconductor detector has been developed for the investigation of molecular ionization and fragmentation processes in strong laser fields. Used as a part of a velocity map imaging spectrometer, the detection system is comprised of a set of microchannel plates and a Timepix detector. A fast time-to-digital converter (TDC) is used to enhance the ion time-of-flight resolution by correlating timestamps registered separately by the Timepix detector and the TDC. In addition, sub-pixel spatial resolution (<6 μm) is achieved by the use of a center-of-mass centroiding algorithm. This performance is achieved while retaining a high event rate (104 per s). The spectrometer was characterized and used in a proof-of-principle experiment on strong field dissociative double ionization of carbon dioxide molecules (CO2), using a 400 kHz repetition rate laser system. The experimental results demonstrate that the spectrometer can detect multiple ions in coincidence, making it a valuable tool for studying the fragmentation dynamics of molecules in strong laser fields.

Probing nuclear dynamics of oriented HeH+ with odd-even high-order harmonics

We study the electron-nuclear coupled dynamics for oriented ${\mathrm{HeH}}^{+}$ molecules in strong laser fields numerically and analytically. At small orientation angles, the asymmetric molecule tends to stretch to distances larger than the equilibrium separation and strong even harmonics are emitted. We show that the permanent dipole of the system plays an important role in the vibrational dynamics of the nuclear wave packet. The nuclear motion and the molecular structure can be read from the spectra and ellipticity of odd-even high harmonics. Our results also have implications for strong-field ionization of the asymmetric system.

Electronic dynamics of charge resonance enhanced ionization probed by laser-induced alignment in C2H2

Although charge resonance enhanced ionization (CREI) be an ubiquitous effect in molecules in strong laser fields, the associated electron emission remains difficult to deal with. The main reason relies on the fact that CREI is part of an overall multielectron ionization, where the initial steps of single and dissociative ionization of neutral species dominate the electron spectrum. Using the rescattered electrons, we show that it is possible to address the electron signal from CREI without any contribution from other electron signals. The electrons from CREI are preferentially emitted when the molecular axis is parallel to the laser electric field as expected from its electronic dynamics. Acetylene is chosen for demonstration purpose because single ionization, which is not related to CREI, is more pronounced when the C2H2 molecular axis is perpendicular to the laser electric field.