Probing Molecular Dynamics by Laser-Induced Backscattering Holography.

We use differential holography to overcome the forward scattering problem in strong-field photoelectron holography. Our differential holograms of H_{2} and D_{2} molecules exhibit a fishbonelike structure, which arises from the backscattered part of the recolliding photoelectron wave packet. We demonstrate that the backscattering hologram can resolve the different nuclear dynamics between H_{2} and D_{2} with subangstrom spatial and subcycle temporal resolution. In addition, we show that attosecond electron dynamics can be resolved. These results open a new avenue for ultrafast studies of molecular dynamics in small molecules.

Nonclassical correlations between terahertz-bandwidth photons mediated by rotational quanta in hydrogen molecules.

Quantum photonics offers much promise for the development of new technologies. The ability to control the interaction of light and matter at the level of single quantum excitations is a prerequisite for the construction of potentially powerful devices. Here we use the rotational levels of a room temperature ensemble of hydrogen molecules to couple two distinct optical modes at the single photon level using femtosecond pulses with 2 THz bandwidth. We observe photon correlations that violate a Cauchy-Schwarz inequality, thereby verifying the creation of a nonclassical state. This work demonstrates the rich potential of molecules for use in ultrafast quantum photonic devices.

Tabletop imaging of structural evolutions in chemical reactions demonstrated for the acetylene cation.

The introduction of femto-chemistry has made it a primary goal to follow the nuclear and electronic evolution of a molecule in time and space as it undergoes a chemical reaction. Using Coulomb Explosion Imaging, we have shot the first high-resolution molecular movie of a to and fro isomerization process in the acetylene cation. So far, this kind of phenomenon could only be observed using vacuum ultraviolet light from a free-electron laser. Here we show that 266 nm ultrashort laser pulses are capable of initiating rich dynamics through multiphoton ionization. With our generally applicable tabletop approach that can be used for other small organic molecules, we have investigated two basic chemical reactions simultaneously: proton migration and C=C bond breaking, triggered by multiphoton ionization. The experimental results are in excellent agreement with the timescales and relaxation pathways predicted by new and quantitative ab initio trajectory simulations.

Excited state dynamics in SO2. I. Bound state relaxation studied by time-resolved photoelectron-photoion coincidence spectroscopy.

The excited state dynamics of isolated sulfur dioxide molecules have been investigated using the time-resolved photoelectron spectroscopy and time-resolved photoelectron-photoion coincidence techniques. Excited state wavepackets were prepared in the spectroscopically complex, electronically mixed (B̃)(1)B1/(Ã)(1)A2, Clements manifold following broadband excitation at a range of photon energies between 4.03 eV and 4.28 eV (308 nm and 290 nm, respectively). The resulting wavepacket dynamics were monitored using a multiphoton ionisation probe. The extensive literature associated with the Clements bands has been summarised and a detailed time domain description of the ultrafast relaxation pathways occurring from the optically bright (B̃)(1)B1 diabatic state is presented. Signatures of the oscillatory motion on the (B̃)(1)B1/(Ã)(1)A2 lower adiabatic surface responsible for the Clements band structure were observed. The recorded spectra also indicate that a component of the excited state wavepacket undergoes intersystem crossing from the Clements manifold to the underlying triplet states on a sub-picosecond time scale. Photoelectron signal growth time constants have been predominantly associated with intersystem crossing to the (c̃)(3)B2 state and were measured to vary between 750 and 150 fs over the implemented pump photon energy range. Additionally, pump beam intensity studies were performed. These experiments highlighted parallel relaxation processes that occurred at the one- and two-pump-photon levels of excitation on similar time scales, obscuring the Clements band dynamics when high pump beam intensities were implemented. Hence, the Clements band dynamics may be difficult to disentangle from higher order processes when ultrashort laser pulses and less-differential probe techniques are implemented.

Ultrafast relaxation dynamics of uracil probed via strong field dissociative ionization.

We study the ultrafast relaxation dynamics of uracil excited to the first bright ππ* state (S2) by an ultrafast laser pulse in the deep ultraviolet (central wavelength λ0 = 260 nm). With a unique combination of strong field dissociative ionization measurements, state of the art strong field ionization calculations, and high level ab initio calculations of excited neutral and ionic states at critical points along the neutral potentials, we are able to gain a detailed picture of the relaxation dynamics of the molecule, which resolves earlier disagreements regarding measurements and calculations of the relaxation.

Channel- and angle-resolved above threshold ionization in the molecular frame.

In strong-field ionization (SFI) of polyatomic molecules, the participation of multiple electronic ionization channels is emerging as a key aspect. In the molecular frame, each channel is expected to show a characteristic dependence of the SFI yield on the polarization direction of the ionizing field. We apply a new angle- and channel-resolved SFI technique to the polyatomic molecule 1,3-butadiene and compare these molecular-frame measurements with two leading theoretical models.

Quantum random bit generation using energy fluctuations in stimulated Raman scattering.

Random number sequences are a critical resource in modern information processing systems, with applications in cryptography, numerical simulation, and data sampling. We introduce a quantum random number generator based on the measurement of pulse energy quantum fluctuations in Stokes light generated by spontaneously-initiated stimulated Raman scattering. Bright Stokes pulse energy fluctuations up to five times the mean energy are measured with fast photodiodes and converted to unbiased random binary strings. Since the pulse energy is a continuous variable, multiple bits can be extracted from a single measurement. Our approach can be generalized to a wide range of Raman active materials; here we demonstrate a prototype using the optical phonon line in bulk diamond.

Neutral-ionic state correlations in strong-field molecular ionization.

We study correlations between neutral and ionic states in strong-field molecular ionization. We compare predictions based on Dyson orbital norms and quasistatic semiclassical tunneling theories (Keldysh and molecular orbital Ammosov-Delone-Krainov) with more detailed calculations of strong-field ionization which take into account (i) the Coulomb interaction between the outgoing continuum electron wave packet and the remaining bound electrons and (ii) electron-core interactions that cause distortions of the electronic continuum states during the ionization event. Our results highlight the prominence of electronic rearrangement effects in strong-field ionization with intense ultrafast laser pulses, where the outgoing continuum electron can cause electronic transitions in the parent ion. Calculations and measurements for excited uracil molecules reveal the breakdown of Keldysh-weighted Dyson norm predictions for ionization to different states of the molecular cation in the strong-field regime.

Mechanisms of two-color laser-induced field-free molecular orientation.

Two mechanisms of two-color (ω+2ω) laser-induced field-free molecular orientation, based on the hyperpolarizability and ionization depletion, are explored and compared. The CO molecule is used as a computational example. While the hyperpolarizability mechanism generates small amounts of orientation at intensities below the ionization threshold, ionization depletion quickly becomes the dominant mechanism as soon as ionizing intensities are reached. Only the ionization mechanism leads to substantial orientation (e.g., on the order of ≳0.1). For intensities typical of laser-induced molecular alignment and orientation experiments, the two mechanisms lead to robust, characteristic timings of the field-free orientation wave-packet revivals relative to the alignment revivals and the revival time. The revival timings can be used to detect the active orientation mechanism experimentally.

The multielectron ionization dynamics underlying attosecond strong-field spectroscopies.

Subcycle strong-field ionization (SFI) underlies many emerging spectroscopic probes of atomic or molecular attosecond electronic dynamics. Extending methods such as attosecond high harmonic generation spectroscopy to complex polyatomic molecules requires an understanding of multielectronic excitations, already hinted at by theoretical modeling of experiments on atoms, diatomics, and triatomics. Here, we present a direct method which, independent of theory, experimentally probes the participation of multiple electronic continua in the SFI dynamics of polyatomic molecules. We use saturated (n-butane) and unsaturated (1,3-butadiene) linear hydrocarbons to show how subcycle SFI of polyatomics can be directly resolved into its distinct electronic-continuum channels by above-threshold ionization photoelectron spectroscopy. Our approach makes use of photoelectron-photofragment coincidences, suiting broad classes of polyatomic molecules.

Tunnel ionization of molecules and orbital imaging.

We study whether tunnel ionization of aligned molecules can be used to map out the electronic structure of the ionizing orbitals. We show that the common view, which associates tunnel ionization rates with the electronic density profile of the ionizing orbital, is not always correct. Using the example of tunnel ionization from the CO(2) molecule, we show how and why the angular structure of the alignment-dependent ionization rate moves with increasing the strength of the electric field. These modifications reflect a general trend for molecules.

Communication: Conditions for one-photon coherent phase control in isolated and open quantum systems.

Coherent control of observables using the phase properties of weak light that induces one-photon transitions is considered. Measurable properties are shown to be categorizable as either class A, where control is not possible, or class B, where control is possible. Using formal arguments, we show that phase control in open systems can be environmentally assisted.

Direct XUV probing of attosecond electron recollision.

We demonstrate that the recolliding electron wave packet, fundamental to many strong field phenomena, can be directly imaged with sub-A spatial and attosecond temporal resolution using attosecond extreme ultraviolet (XUV) pulses. When the recolliding electron revisits the parent ion, it can absorb an XUV photon yielding high energy electron and thereby providing a measurement of the electron energy at the moment of recollision. The full temporal evolution of the recollision wave packet can be reconstructed by measuring the photoelectron spectra for different time delays between the driving laser and the attosecond XUV probe. The strength of the photoelectron signal can be used to characterize the spatial distribution of the electron density in the longitudinal direction. Elliptical polarization can be used to characterize the electron probability in transversal direction.

Controlling high harmonic generation with molecular wave packets.

We show that, by controlling the alignment of molecules, we can influence the high harmonic generation process. We observed strong intensity modulation and spectral shaping of high harmonics produced with a rotational wave packet in a low-density gas of N2 or O2. In N2, where the highest occupied molecular orbital (HOMO) has sigma(g) symmetry, the maximum signal occurs when the molecules are aligned along the laser polarization while the minimum occurs when it is perpendicular. In O2, where the HOMO has pi(g) symmetry, the harmonics are enhanced when the molecules are aligned around 45 degrees to the laser polarization. The symmetry of the molecular orbital can be read by harmonics. Molecular wave packets offer a means of shaping attosecond pulses.

Is the Filinov integral conditioning technique useful in semiclassical initial value representation methods?

The utility of the Filinov integral conditioning technique, as implemented in semiclassical initial value representation (SC-IVR) methods, is analyzed for a number of regular and chaotic systems. For nonchaotic systems of low dimensionality, the Filinov technique is found to be quite ineffective at accelerating convergence of semiclassical calculations since, contrary to the conventional wisdom, the semiclassical integrands usually do not exhibit significant phase oscillations in regions of large integrand amplitude. In the case of chaotic dynamics, it is found that the regular component is accurately represented by the SC-IVR, even when using the Filinov integral conditioning technique, but that quantum manifestations of chaotic behavior was easily overdamped by the filtering technique. Finally, it is shown that the level of approximation introduced by the Filinov filter is, in general, comparable to the simpler ad hoc truncation procedure introduced by Kay.

Coherent control of rotational wave-packet dynamics via fractional revivals.

We show (i) how the evolution of a wave packet created from an initial thermal ensemble can be controlled by manipulating interferences during the wave packet's fractional revivals and (ii) how the wave-packet evolution can be mapped onto the dynamics of a few-state system, where the number of states is determined by the amount of information one wants to track about the wave packet in the phase space. We illustrate our approach by (i) switching off and on field-free molecular axis alignment induced by a strong laser pulse and (ii) converting alignment into field-free orientation, starting with rotationally cold or hot systems.

Quantum logic approach to wave packet control.

We study control of wave packets with a finite accuracy, approaching it as quantum information processing. For a given control resolution, we define the analogs of several quantum bits within the shape of a single wave packet. These bits are based on wave packet symmetries. Analogs of one- and two-bit gates can be implemented using only free wave packet evolution and coordinate-dependent ac Stark shifts applied at the moments of fractional revivals. As in quantum computation, the gates form a logarithmically small set of basis operations which can be used to approximate any unitary transformation desired for quantum control of the wave packet dynamics. Numerical examples show the application of this approach to control vibrational wave packet revivals.

Molecule without electrons: binding bare nuclei with strong laser fields.

We show how a carefully chosen combination of strong linearly and circularly polarized laser fields can bind two same-sign charges, not only suppressing their Coulomb repulsion in all three spatial dimensions, but also creating an effective attraction. As an example, we show how a molecule HD2+ stripped of both electrons can be kept bound by the laser fields.

Strong field tunnel ionization by real-valued classical trajectories.

Strong field tunnel ionization of an atom is considered from the point of view of semiclassical initial value representation methods which are based on real-valued classical trajectories alone. While the straightforward application of such propagators fails to give an accurate description of tunnel ionization in one dimension, incorporating the semiclassical propagator into S-matrix techniques standard in strong field physics leads to a more accurate method which recovers the tunneling dynamics. From the point of view of strong field physics, this procedure offers a method of incorporating core effects into the standard strong field approximation. In two dimensions, both the standard and the new semiclassical propagators are shown to give equally accurate results at sufficiently short times, but the new method exhibits much better scaling of the convergence rate with increasing dimensionality.