Exploring the ultrafast and isomer-dependent photodissociation of iodothiophenes via site-selective ionization.

C-I bond extension and fission following ultraviolet (UV, 262 nm) photoexcitation of 2- and 3-iodothiophene is studied using ultrafast time-resolved extreme ultraviolet (XUV) ionization in conjunction with velocity map ion imaging. The photoexcited molecules and eventual I atom products are probed by site-selective ionization at the I 4d edge using intense XUV pulses, which induce multiple charges initially localized to the iodine atom. At C-I separations below the critical distance for charge transfer (CT), charge can redistribute around the molecule leading to Coulomb explosion and charged fragments with high kinetic energy. At greater C-I separations, beyond the critical distance, CT is no longer possible and the measured kinetic energies of the charged iodine atoms report on the neutral dissociation process. The time and momentum resolved measurements allow determination of the timescales and the respective product momentum and kinetic energy distributions for both isomers, which are interpreted in terms of rival 'direct' and 'indirect' dissociation pathways. The measurements are compared with a classical over the barrier model, which reveals that the onset of the indirect dissociation process is delayed by ∼1 ps relative to the direct process. The kinetics of the two processes show no discernible difference between the two parent isomers, but the branching between the direct and indirect dissociation channels and the respective product momentum distributions show isomer dependencies. The greater relative yield of indirect dissociation products from 262 nm photolysis of 3-iodothiophene (cf. 2-iodothiophene) is attributed to the different partial cross-sections for (ring-centred) π∗ ← π and (C-I bond localized) σ∗ ← (n/π) excitation in the respective parent isomers.

Stronger orientation of state-selected OCS molecules with relative-delay-adjusted nanosecond two-color laser pulses.

Using the all-optical molecular orientation technique with intense nonresonant two-color laser pulses, stronger molecular orientation |⟨cos θ2D⟩| ∼ 0.34 is achieved by employing the following two strategies: (1) carbonyl sulfide molecules lying in the lower rotational states are selected using a home-built molecular deflector and (2) the rising parts of the two wavelengths of the pump pulse are adjusted by introducing a Michelson-type delay line in the optical path. The achieved degree of molecular orientation is higher than that observed in the proof-of-principle experiment [Oda et al., Phys. Rev. Lett. 104, 213901 (2010)] by about an order of magnitude and the highest ever characterized directly by Coulomb explosion imaging with appropriate probe polarization.

Development of a plasma shutter applicable to 100-mJ-class, 10-ns laser pulses and the characterization of its performance.

For the purpose of preparing a sample of aligned and oriented molecules in the laser-field-free condition, we developed a plasma shutter, which enables laser pulses with 100-mJ-class, 10-ns pulse durations to be rapidly turned off within ∼150 fs. Inthis work, the residual field intensity after the rapid turn off is carefully examined by applying the shaped laser pulse to OCS molecules in the rotational ground state. Based on the comparison between the observation of alignment revivals of the OCS molecules and the results of numerical simulations, we demonstrate that the residual field intensity is actually negligible (below 0.4% of the peak intensity) and, if any, does not influence the alignment and orientation dynamics at all.

Quantum interference during high-order harmonic generation from aligned molecules.

High-order harmonic generation (HHG) from atoms and molecules offers potential application as a coherent ultrashort radiation source in the extreme ultraviolet and soft X-ray regions. In the three-step model of HHG, an electron tunnels out from the atom and may recombine with the parent ion (emitting a high-energy photon) after undergoing laser-driven motion in the continuum. Aligned molecules can be used to study quantum phenomena in HHG associated with molecular symmetries; in particular, simultaneous observations of both ion yields and harmonic signals under the same conditions serve to disentangle the contributions from the ionization and recombination processes. Here we report evidence for quantum interference of electron de Broglie waves in the recombination process of HHG from aligned CO2 molecules. The interference takes place within a single molecule and within one optical cycle. Characteristic modulation patterns of the harmonic signals measured as a function of the pump-probe delay are explained with simple formulae determined by the valence orbital of the molecules. We propose that simultaneous observations of both ion yields and harmonic signals can serve as a new route to probe the instantaneous structure of molecular systems.

Measuring polarizability anisotropies of rare gas diatomic molecules by laser-induced molecular alignment technique.

The polarizability anisotropies of homonuclear rare gas diatomic molecules, Ar(2), Kr(2), and Xe(2), are investigated by utilizing the interaction of the induced electric dipole moment with a nonresonant, nanosecond laser pulse. The degree of alignment, which depends on the depth of the interaction potential created by the intense laser field, is measured, and is found to increase in order of Ar(2), Kr(2), and Xe(2) at the same peak intensity. Compared with a reference I(2) molecule, Ar(2), Kr(2), and Xe(2) are found to have the polarizability anisotropies of 0.45 ± 0.13, 0.72 ± 0.13, and 1.23 ± 0.21 Å(3), respectively, where the uncertainties (one standard deviation) in the polarizability anisotropies are carefully evaluated on the basis of the laser intensity dependence of the degree of alignment. The obtained values are compared with recent theoretical calculations and are found to agree well within the experimental uncertainties.

All-optical molecular orientation.

We report clear evidence of all-optical orientation of carbonyl sulfide molecules with an intense nonresonant two-color laser field in the adiabatic regime. The technique relies on the combined effects of anisotropic hyperpolarizability interaction and anisotropic polarizability interaction and does not rely on the permanent dipole interaction with an electrostatic field. It is demonstrated that the molecular orientation can be controlled simply by changing the relative phase between the two wavelength fields. The present technique brings researchers a new steering tool of gaseous molecules and will be quite useful in various fields such as electronic stereodynamics in molecules and ultrafast molecular imaging.

Structure determination of molecules in an alignment laser field by femtosecond photoelectron diffraction using an X-ray free-electron laser.

We have successfully determined the internuclear distance of I2 molecules in an alignment laser field by applying our molecular structure determination methodology to an I 2p X-ray photoelectron diffraction profile observed with femtosecond X-ray free electron laser pulses. Using this methodology, we have found that the internuclear distance of the sample I2 molecules in an alignment Nd:YAG laser field of 6 × 1011 W/cm2 is elongated by from 0.18 to 0.30 Å "in average" relatively to the equilibrium internuclear distance of 2.666 Å. Thus, the present experiment constitutes a critical step towards the goal of femtosecond imaging of chemical reactions and opens a new direction for the study of ultrafast chemical reaction in the gas phase.

Photoelectron diffraction from laser-aligned molecules with X-ray free-electron laser pulses.

We report on the measurement of deep inner-shell 2p X-ray photoelectron diffraction (XPD) patterns from laser-aligned I2 molecules using X-ray free-electron laser (XFEL) pulses. The XPD patterns of the I2 molecules, aligned parallel to the polarization vector of the XFEL, were well matched with our theoretical calculations. Further, we propose a criterion for applying our molecular-structure-determination methodology to the experimental XPD data. In turn, we have demonstrated that this approach is a significant step toward the time-resolved imaging of molecular structures.

Optimal control of nonadiabatic alignment of rotationally cold N2 molecules with the feedback of degree of alignment.

Nonadiabatic alignment of rotationally cold N2 molecules is optimally controlled by shaping femtosecond pump pulses with the feedback of degree of alignment evaluated by an ion imaging technique. The alignment is optimized by doubly peaked pulses with approximately equal intensities. A doubly peaked pulse with an appropriate interval can be regarded as a single pulse with a center trough based on the considerations from both time and frequency domains, suggesting that the effective duration of a doubly peaked pulse rather than its structure is crucial to nonadiabatic molecular alignment.

Laser-field-free molecular orientation.

We demonstrate laser-field-free molecular orientation with the combination of a moderate electrostatic field and an intense nonresonant rapidly turned-off laser field, which can be shaped with the plasma shutter technique. We use OCS (carbonyl sulfide) molecules as a sample. Molecular orientation is adiabatically created in the rising part of the laser pulse, and it is found to revive at around the rotational period of an OCS molecule with the same degree of orientation as that at the peak of the laser pulse in the virtually laser-field-free condition. This accomplishment means that a new class of molecular sample has become available for various applications.

Ellipticity dependence of high-order harmonic generation from aligned molecules.

We report ellipticity dependence of high-order harmonic generation (HHG) from aligned N2, O2, and CO2 molecules. Experimentally, we find that the ellipticity dependence is sensitive to molecular alignment and to the shape and symmetry of the valence orbitals. It is also found that the destructive interference in the recombination process affects the ellipticity dependence. Theoretically, we extend the original Lewenstein model to a more generalized model, which can be applicable to HHG from molecules, by introducing an electron acceleration parameter xi(theta) and by combining the molecular orbital method. The present observations are successfully explained by our model.

Nontrivial polarization shaping of femtosecond pulses by reference to the results of dual-channel spectral interferometry.

Adaptive shaping of time-dependent polarization pulses is performed by reference to the analyzed results of dual-channel spectral interferometry. The desired pulses can be generated only by use of such a polarization-characterization technique. We demonstrate the generation of shaped femtosecond pulses whose ellipticity increases at a constant rate. The relative error between the shaped pulse and the target pulse is less than 6% over the main part of the pulse. Shaped time-dependent polarization pulses have many potential applications.

Optimal control of multiphoton ionization processes in aligned I2 molecules with time-dependent polarization pulses.

Multiphoton ionization processes in aligned I2 molecules are actively controlled by the homemade pulse shaping system, with which a time-dependent polarization pulse can be generated and controlled. We find a correlation between a femtosecond time-dependent polarization pulse and the production efficiency of evenly or oddly charged molecular ions. We achieve much better controllability of the correlation with a time-dependent polarization pulse than with a pulse having a fixed ellipticity. The results suggest the existence of an unknown tunnel ionization mechanism which is characteristic of a time-dependent polarization pulse. Our experiments point to new directions in optimal control studies with molecular systems, as discussed in the text.

Controlling the orientation of polar molecules with combined electrostatic and pulsed, nonresonant laser fields.

We demonstrate that molecules with a moderate permanent dipole moment can be oriented with combined electrostatic and pulsed, nonresonant laser fields. We use OCS molecules as a sample. The degree of orientation can be increased by increasing the magnitude of electrostatic field and the peak intensity of the laser field or by decreasing the rotational temperature of the molecules.