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Vibrational wave packets are created in the lowest triplet state \triplet of $\mathrm{K_2}$ and $\mathrm{Rb_2}$ residing on the surface of helium nanodroplets, through non-resonant stimulated impulsive Raman scattering induced by a moderately intense near-infrared laser pulse. A delayed, intense 50-fs laser pulse doubly ionizes the alkali dimers via multiphoton absorption and thereby causes them to Coulomb explode into a pair of alkali ions $\mathrm{Ak^+}$. From the kinetic energy distribution $P(E_\mathrm{kin})$ of the $\mathrm{Ak^+}$ fragment ions, measured at a large number of delays, we determine the time-dependent internuclear distribution $P(R,t)$, which represents the modulus square of the wave packet within the accuracy of the experiment. For both $\mathrm{K_2}$ and $\mathrm{Rb_2}$, $P(R,t)$ exhibits a periodic oscillatory structure throughout the respective 300 ps and 100 ps observation times. The oscillatory structure is reflected in the time-dependent mean value of $R$, $\langle R \rangle(t)$. Fourier transformation of $\langle R \rangle(t)$ shows that the wave packets are composed mainly of the vibrational ground state and the first excited vibrational state, in agreement with numerical simulations. In the case of $\mathrm{K_2}$, the oscillations are observed for 300 ps corresponding to more than 180 vibrational periods with an amplitude that decreases gradually from 0.035 {\AA} to 0.020 {\AA}. Using time-resolved spectral analysis, we find that the decay time of the amplitude is $\sim$ 260 ps. The decrease is ascribed to the weak coupling between the vibrating dimers and the droplet.

Alkali trimers, Ak$_3$, located on the surface of He nanodroplets are triply ionized following multiphoton absorption from an intense femtosecond laser pulse leading to fragmentation into three correlated Ak$^+$ ions. Combining the information from three-fold covariance analysis of the emission direction of the fragment ions and from their kinetic energy distributions $P(E_{\text{kin}})$, we find that Na$_3$, K$_3$, and Rb$_3$ have an equilateral triangular structure, corresponding to that of the lowest-lying quartet state $^{4}\mathrm{A}_{2}'$, and determine the equilibrium bond distance $R_\text{eq}$(Na$_3$) = 4.65 $\pm$ 0.15 {\AA}, $R_\text{eq}$(K$_3$) = 5.03 $\pm$ 0.18 {\AA}, and $R_\text{eq}$(Rb$_3$) = 5.45 $\pm$ 0.22 {\AA}. For K$_3$ and Rb$_3$ these values agree well with existing theoretical calculations, while for Na$_3$ the value is 0.2-0.3 {\AA} larger than the existing theoretical results. The discrepancy is ascribed to a minor internuclear motion of Na$_3$ during the ionization process. Also, we determine the distribution of internuclear distances $P(R)$ under the assumption of fixed bond angles. The results are compared to the square of the internuclear wave function $|\Psi(R)|^2$., Comment: 7 pages, 5 figures

We demonstrate that a sodium dimer, Na$_{2}$($1^3\Sigma_{u}^+$), residing on the surface of a helium nanodroplet, can be set into rotation by a nonresonant 1.0 ps infrared laser pulse. The time-dependent degree of alignment measured, exhibits a periodic, gradually decreasing structure that deviates qualitatively from that expected for gas phase dimers. Comparison to alignment dynamics calculated from the time-dependent rotational Schr\"{o}dinger equation shows that the deviation is due to the alignment dependent interaction between the dimer and the droplet surface. This interaction confines the dimer to the tangential plane of the droplet surface at the point where it resides and is the reason that the observed alignment dynamics is also well-described by a 2D quantum rotor model., Comment: 6 pages, 4 figures

Superfluid helium nanodroplets are an ideal environment for the formation of metastable, self-organized dopant nanostructures. However, the presence of vortices often hinders their formation. Here, we demonstrate the generation of vortex-free helium nanodroplets and explore the size range in which they can be produced. From x-ray diffraction images of xenon-doped droplets, we identify that single compact structures, assigned to vortex-free aggregation, prevail up to $10^8$ atoms per droplet. This finding builds the basis for exploring the assembly of far-from-equilibrium nanostructures at low temperatures., Comment: main article: 7 pages, 3 figures; supplementary material: 12 pages, 8 figures

Alkali dimers, $\mathrm{Ak}_2$, residing on the surface of He nanodroplets are doubly ionized due to multiphoton absorption from an intense, 50-fs laser pulse leading to fragmentation into a pair of alkali cations. Based on the measured kinetic energy distributions, $P(E_{\text{kin}})$, of the $\mathrm{Ak}^+$ fragment ions, we retrieve the distribution of internuclear distances, $P(R)$, via the $\mathrm{Ak}_2^{2+}$ potential curve. Results are obtained for $\mathrm{{Na}_2}$, $\mathrm{K}_2$, $\mathrm{Rb}_2$, and $\mathrm{Cs}_2$ in both the 1 $^1\Sigma_{g}^+$ ground state and in the lowest-lying triplet state 1 $^3\Sigma_{u}^+$, and for $\mathrm{Li}_2$ in the 1 $^3\Sigma_{u}^+$ state. For $\mathrm{Li}_2$, $\mathrm{K}_2$, and $\mathrm{Rb}_2$, the center of the measured $P(R)$'s is close to the center of the wave function, $\Psi(R)$, of the vibrational ground state in the 1 $^1\Sigma_{g}^+$ and 1 $^3\Sigma_{u}^+$ states, whereas for $\mathrm{{Na}_2}$ and $\mathrm{{Cs}_2}$ small shifts are observed. For all the $\mathrm{{Ak}_2}$, the width of the measured $P(R)$ is broader than $|\Psi(R)|^2$ by a factor of 2-4. We discuss that resonance effects in the multiphoton ionization and interaction of the $\mathrm{Ak}^+$ ion with the He droplet give rise to the observed deviations of $P(R)$ from $|\Psi(R)|^2$. Despite these deviations, we deem that timed Coulomb explosion will allow imaging of vibrational wave packets in alkali dimers on He droplets surfaces., Comment: 10 pages, 6 figures

We present a simple quantum mechanical model describing excited rotational states of molecules in superfluid helium nanodroplets, as recently studied in non-adiabatic molecular alignment experiments [Cherepanov et al., Phys. Rev. A 104, L061303 (2021)]. We show that a linear molecule immersed in a superfluid can be seen as an effective symmetric top, similar to the rotational structure of radicals, such as OH or NO, but with the angular momentum of the superfluid playing the role of the electronic angular momentum in free molecules. The model allows to evaluate the effective rotational and centrifugal distortion constants for a broad range of species and to explain the crossover between light and heavy molecules in superfluid $^4$He in terms of the many-body wavefunction structure. Most important, the simple theory allows to answer the question as to what happens when the rotational angular momentum of the molecule increases beyond the lowest excited states accessible by infrared spectroscopy. Some of the above mentioned insights can be acquired by analyzing a simple 2x2 matrix.

Rotational dynamics of D$_2$ molecules inside helium nanodroplets is induced by a moderately intense femtosecond (fs) pump pulse and measured as a function of time by recording the yield of HeD$^+$ ions, created through strong-field dissociative ionization with a delayed fs probe pulse. The yield oscillates with a period of 185 fs, reflecting field-free rotational wave packet dynamics, and the oscillation persists for more than 500 periods. Within the experimental uncertainty, the rotational constant BHe of the in-droplet D$_2$ molecule, determined by Fourier analysis, is the same as Bgas for an isolated D$_2$ molecule. Our observations show that the D$_2$ molecules inside helium nanodroplets essentially rotate as free D$_2$ molecules.

Rubidium dimers residing on the surface of He nanodroplets are doubly ionized by an intense fs laser pulse leading to fragmentation into a pair of $\mathrm{Rb^+}$ ions. We show that the kinetic energy of the $\mathrm{Rb^+}$ fragment ions can be used to identify dimers formed in either the X $^1\Sigma_{\mathrm{g}}^+$ ground state or in the lowest-lying triplet state, a $^3\Sigma_{\mathrm{u}}^+$. From the experiment, we estimate the abundance ratio of dimers in the a and X states as a function of the mean droplet size and find values between 4:1 and 5:1. Our technique applies generally to dimers and trimers of alkali atoms, here also demonstrated for $\mathrm{Li_2}$, $\mathrm{Na_2}$, and $\mathrm{K_2}$, and will enable fs time-resolved measurements of their rotational and vibrational dynamics, possibly with atomic structural resolution., Comment: 5 pages, 4 figures

We combine experimental and theoretical approaches to explore excited rotational states of molecules embedded in helium nanodroplets using CS$_2$ and I$_2$ as examples. Laser-induced nonadiabatic molecular alignment is employed to measure spectral lines for rotational states extending beyond those initially populated at the 0.37 K droplet temperature. We construct a simple quantum mechanical model, based on a linear rotor coupled to a single-mode bosonic bath, to determine the rotational energy structure in its entirety. The calculated and measured spectral lines are in good agreement. We show that the effect of the surrounding superfluid on molecular rotation can be rationalized by a single quantity -- the angular momentum, transferred from the molecule to the droplet., Comment: 5 pages, 4 figures; 5 pages, 3 figures

We have deduced the structure of the \ce{bromobenzene}--\ce{I2} heterodimer and the \ce{(bromobenzene)2} homodimer inside helium droplets using a combination of laser-induced alignment, Coulomb explosion imaging, and three-dimensional ion imaging. The complexes were fixed in a variety of orientations in the laboratory frame, then in each case multiply ionized by an intense laser pulse. A three dimensional ion imaging detector, including a Timepix3 detector allowed us to measure the correlations between velocity vectors of different fragments and, in conjunction with classical simulations, work backward to the initial structure of the complex prior to explosion. For the heterodimer, we find that the \ce{I2} molecular axis intersects the phenyl ring of the bromobenzene approximately perpendicularly. The homodimer has a stacked parallel structure, with the two bromine atoms pointing in opposite directions. These results illustrate the ability of Coulomb explosion imaging to determine the structure of large complexes, and point the way toward real-time measurements of bimolecular reactions inside helium droplets.

Radiation-induced damage of biological matter is an ubiquitous problem in nature. The influence of the hydration environment is widely discussed, but its exact role remains elusive. Utilising well defined solvated-molecule aggregates, we experimentally observed a hydrogen-bonded water molecule acting as a radiation protection agent for ionised pyrrole, a prototypical aromatic biomolecule. Pure samples of pyrrole and pyrrole(H$_2$O) were outer-valence ionised and the subsequent damage and relaxation processes were studied. Bare pyrrole ions fragmented through the breaking of C-C or N-C covalent bonds. However, for pyrrole(H$_2$O)$^+$, we observed a strong protection of the pyrrole ring through the dissociative release of neutral water or by transferring an electron or proton across the hydrogen bond. Overall, a single water molecule strongly reduces the fragmentation probability and thus the persistent radiation damage of singly-ionised pyrrole., Comment: 15 pages, 8 figures

Alignment of OCS, CS$_2$ and I$_2$ molecules embedded in helium nanodroplets is measured as a function of time following rotational excitation by a non-resonant, comparatively weak ps laser pulse. The distinct peaks in the power spectra, obtained by Fourier analysis, are used to determine the rotational, B, and centrifugal distortion, D, constants. For OCS, B and D match the values known from IR spectroscopy. For CS$_2$ and I$_2$, they are the first experimental results reported. The alignment dynamics calculated from the gas-phase rotational Schr\"{o}dinger equation, using the experimental in-droplet B and D values, agree in detail with the measurement for all three molecules. The rotational spectroscopy technique for molecules in helium droplets introduced here should apply to a range of molecules and complexes., Comment: ASC and LC contributed equally. 7 pages, 3 figures

We report experimental results on the diffractive imaging of three-dimensionally aligned 2,5-diiodothiophene molecules. The molecules were aligned by chirped near-infrared laser pulses, and their structure was probed at a photon energy of 9.5 keV ($\lambda\approx130 \text{pm}$) provided by the Linac Coherent Light Source. Diffracted photons were recorded on the CSPAD detector and a two-dimensional diffraction pattern of the equilibrium structure of 2,5-diiodothiophene was recorded. The retrieved distance between the two iodine atoms agrees with the quantum-chemically calculated molecular structure to within 5 %. The experimental approach allows for the imaging of intrinsic molecular dynamics in the molecular frame, albeit this requires more experimental data which should be readily available at upcoming high-repetition-rate facilities.

Dimers of tetracene molecules are formed inside helium nanodroplets and identified through covariance analysis of the emission directions of kinetic tetracene cations stemming from femtosecond laser-induced Coulomb explosion. Next, the dimers are aligned in either one or three dimensions under field-free conditions by a nonresonant, moderately intense laser pulse. The experimental angular covariance maps of the tetracene ions are compared to calculated covariance maps for seven different dimer conformations and found to be consistent with four of these. Additional measurements of the alignment-dependent strong-field ionization yield of the dimer narrows the possible conformations down to either a slipped-parallel or parallel-slightly-rotated structure. According to our quantum chemistry calculations, these are the two most stable gas-phase conformations of the dimer and one of them is favorable for singlet fission.

We use laser-induced rotation of single molecules embedded in superfluid helium nanodroplets to reveal angular momentum dynamics and transfer in a controlled setting, under far-from-equilibrium conditions. As an unexpected result, we observe pronounced oscillations of time-dependent molecular alignment that have no counterpart in gas-phase molecules. Angulon theory reveals that these oscillations originate from the unique rotational structure of molecules in He droplets and quantum-state-specific transfer of rotational angular momentum to the many-body He environment on picosecond timescales. Our results pave the way to understanding collective effects of macroscopic angular momentum exchange in solid state systems in a bottom-up fashion., Comment: 5+9 pages, 3+1 figures

Measurements on the strong-field ionization of carbonyl sulfide molecules by short, intense, 2~\um wavelength laser pulses are presented from experiments where angle-resolved photoelectron distributions were recorded with a high-energy velocity map imaging spectrometer, designed to reach a maximum kinetic energy of 500~eV. The laser-field-free elastic-scattering cross section of carbonyl sulfide was extracted from the measurements and is found in good agreement with previous experiments, performed using conventional electron diffraction. By comparing our measurements to the results of calculations, based on the quantitative rescattering theory (QRS), the bond lengths and molecular geometry were extracted from the experimental differential cross sections to a precision better than $\pm5$~pm and in agreement with the known values.

The gas-phase structures of four difluoroiodobenzene and two dihydroxybromobenzene isomers were identified by correlating the emission angles of atomic fragment ions created following femtosecond laser-induced Coulomb explosion. The structural determinations were facilitated by confining the most polarizable axis of each molecule to the detection plane prior to the Coulomb explosion event using one-dimensional laser-induced adiabatic alignment. For a molecular target consisting of two difluoroiodobenzene isomers, each constituent structure could additionally be singled out and distinguished., Comment: 13 pages, 4 figures. Published as a communication in the Journal of Chemical Physics

Dimers of carbon disulfide (CS$_2$) molecules embedded in helium nanodroplets are aligned using a moderately intense, 160ps, non-resonant, circularly polarized laser pulse. It is shown that the intermolecular carbon-carbon (C-C) axis aligns along the axis perpendicular to the polarization plane of the alignment laser pulse. The degree of alignment, quantified by $\langle \cos^2(\theta_\text{2D}) \rangle$, is determined from the emission directions of recoiling CS$_2$$^+$ fragment ions, created when an intense 40fs probe laser pulse doubly ionizes the dimers. Here, $\theta_\text{2D}$ is the projection of the angle between the C-C axis on the 2D ion detector and the normal to the polarization plane. $\langle \cos^2(\theta_\text{2D}) \rangle$ is measured as a function of the alignment laser intensity and the results agree well with $\langle \cos^2(\theta_\text{2D}) \rangle$ calculated for gas-phase CS$_2$ dimers with a rotational temperature of 0.4K.

Dimers and trimers of carbonyl sulfide (OCS) molecules embedded in helium nanodroplets are aligned by a linearly polarized 160 ps long moderately intense laser pulse and Coulomb exploded with an intense 40 fs long probe pulse in order to determine their structures. For the dimer, recording of 2D images of OCS$^+$ and S$^+$ ions and covariance analysis of the emission directions of the ions allow us to conclude that the structure is a slipped-parallel shape similar to the structure found for gas phase dimers. For the trimer, the OCS$^+$ ion images and corresponding covariance maps reveal the presence of a barrel-shaped structure (as in gas phase) but also other structures not present in the gas phase, most notably a linear chain structure.

Molecules with their axes sharply confined in space, available through laser-induced alignment methods, are essential for many current experiments, including ultrafast molecular imaging. Most of these applications require both that the aligning laser field is turned-off, to avoid undesired perturbations, and that the molecules remain aligned sufficiently long that reactions and dynamics can be mapped out. Presently, this is only possible for small, linear molecules and for times less than 1 picosecond. Here, we demonstrate strong, field-free alignment of large molecules inside helium nanodroplets, lasting tens of picoseconds. Molecular alignment in either one or three dimensions is created by a slowly switched-on laser pulse, made field-free through rapid pulse truncation, and retained thanks to the impeding effect of the helium environment on molecular rotation. We illustrate the opportunities that field-free aligned molecules open by measuring the alignment-dependent strong-field ionization yield of a thiophene oligomer. Our technique will enable molecular-frame experiments, including ultrafast excited state dynamics, on a variety of large molecules and complexes.

Recording molecular movies on ultrafast timescales has been a longstanding goal for unravelling detailed information about molecular dynamics. We present the direct experimental recording of very-high-resolution and -fidelity molecular movies over more than one-and-a-half periods of the laser-induced rotational dynamics of carbonylsulfide (OCS) molecules. Utilising the combination of single-quantum-state selection and an optimised two-pulse sequence to create a tailored rotational wavepacket, an unprecedented degree of field-free alignment, $\langle \cos^{2}{\theta_{2D}}\rangle=0.96$ ($\langle \cos^{2}{\theta}\rangle=0.94$) was achieved, exceeding the theoretical limit for single-pulse alignment. The very rich experimentally observed quantum dynamics is fully recovered by the angular probability distribution obtained from solutions of the time-dependent Schr\"odinger equation with parameters refined against the experiment. The populations and phases of rotational states in the retrieved time-dependent three-dimensional wavepacket rationalised the observed very high degree of alignment., Comment: 9 Figures

A moderately intense $450$ fs laser pulse is used to create rotational wave packets in gas phase $\rm{I_2}$ molecules. The ensuing time-dependent alignment, measured by Coulomb explosion imaging with a delayed probe pulse, exhibits the characteristic revival structures expected for rotational wave packets but also a complex non-periodic substructure and decreasing mean alignment not observed before. A quantum mechanical model attributes the phenomena to coupling between the rotational angular momenta and the nuclear spins through the electric quadrupole interaction. The calculated alignment trace agrees very well with the experimental results., Comment: 6 pages, 4 figures, and Supplementary Information. This article has been accepted for publication in Physical Review Letters

A new technique for obtaining switched wave packets using spectrally truncated chirped laser pulses is demonstrated experimentally and numerically by one-dimensional alignment of both linear and asymmetric top molecules. Using a simple long-pass transmission filter, a pulse with a slow turn on and a rapid turn off is produced. The degree of alignment, characterized by $\langle\cos^2\theta_\text{2D}\rangle$ rises along with the pulse intensity and reaches a maximum at the peak of the pulse. After truncation $\langle\cos^2\theta_\text{2D}\rangle$ drops sharply but exhibits pronounced half and full revivals. The experimental alignment dynamics trace agrees very well with a numerically calculated trace based on solution of the time-dependent Schr\"odinger equation. However, the extended periods of field-free alignment of asymmetric tops following pulse truncation reported previously is not reproduced in our work., Comment: 7 pages, 4 figures

The dynamics following laser-induced molecular photodissociation of gas-phase CH$_{2}$BrI at 271.6 nm were investigated by time-resolved Coulomb explosion imaging using intense near-IR femtosecond laser pulses. The observed delay-dependent photofragment momenta reveal that CH$_{2}$BrI undergoes C-I cleavage, depositing 65.6% of the available energy into internal product states, and that absorption of a second UV photon breaks the C-Br bond of CH$_{2}$Br. Simulations confirm that this mechanism is consistent with previous data recorded at 248 nm, demonstrating the sensitivity of Coulomb explosion imaging as a real-time probe of chemical dynamics., Comment: 19 pages, 6 figures. Accepted for publication in Physical Review A

We explore time-resolved Coulomb explosion induced by intense, extreme ultraviolet (XUV) femtosecond pulses from the FLASH free-electron laser as a method to image photo-induced molecular dynamics in two molecules, iodomethane and 2,6-difluoroiodobenzene. At an excitation wavelength of 267\,nm, the dominant reaction pathway in both molecules is neutral dissociation via cleavage of the carbon--iodine bond. This allows investigating the influence of the molecular environment on the absorption of an intense, femtosecond XUV pulse and the subsequent Coulomb explosion process. We find that the XUV probe pulse induces local inner-shell ionization of atomic iodine in dissociating iodomethane, in contrast to non-selective ionization of all photofragments in difluoroiodobenzene. The results reveal evidence of electron transfer from methyl and phenyl moieties to a multiply charged iodine ion. In addition, indications for ultrafast charge rearrangement on the phenyl radical are found, suggesting that time-resolved Coulomb explosion imaging is sensitive to the localization of charge in extended molecules.

Laser-induced adiabatic alignment and mixed-field orientation of 2,6-difluoroiodobenzene (C6H3F2I) molecules are probed by Coulomb explosion imaging following either near-infrared strong-field ionization or extreme-ultraviolet multi-photon inner-shell ionization using free-electron laser pulses. The resulting photoelectrons and fragment ions are captured by a double-sided velocity map imaging spectrometer and projected onto two position-sensitive detectors. The ion side of the spectrometer is equipped with the Pixel Imaging Mass Spectrometry (PImMS) camera, a time-stamping pixelated detector that can record the hit positions and arrival times of up to four ions per pixel per acquisition cycle. Thus, the time-of-flight trace and ion momentum distributions for all fragments can be recorded simultaneously. We show that we can obtain a high degree of one- and three-dimensional alignment and mixed- field orientation, and compare the Coulomb explosion process induced at both wavelengths.

Iodine (I$_2$) molecules embedded in He nanodroplets are aligned by a 160 ps long laser pulse. The highest degree of alignment, occurring at the peak of the pulse and quantified by $\langle \cos^2 \theta_{2D} \rangle$, is measured as a function of the laser intensity. The results are well described by $\langle \cos^2 \theta_{2D} \rangle$ calculated for a gas of isolated molecules each with an effective rotational constant of 0.6 times the gas-phase value, and at a temperature of 0.4 K. Theoretical analysis using the angulon quasiparticle to describe rotating molecules in superfluid helium rationalizes why the alignment mechanism is similar to that of isolated molecules with an effective rotational constant. A major advantage of molecules in He droplets is that their 0.4 K temperature leads to stronger alignment than what can generally be achieved for gas phase molecules -- here demonstrated by a direct comparison of the droplet results to measurements on a $\sim$ 1 K supersonic beam of isolated molecules. This point is further illustrated for more complex system by measurements on 1,4-diiodobenzene and 1,4-dibromobenzene. For all three molecular species studied the highest values of $\langle \cos^2 \theta_{2D} \rangle$ achieved in He droplets exceed 0.96., Comment: 11 pages, 8 figures

Rotation of molecules embedded in He nanodroplets is explored by a combination of fs laser-induced alignment experiments and angulon quasiparticle theory. We demonstrate that at low fluence of the fs alignment pulse, the molecule and its solvation shell can be set into coherent collective rotation lasting long enough to form revivals. With increasing fluence, however, the revivals disappear -- instead, rotational dynamics as rapid as for an isolated molecule is observed during the first few picoseconds. Classical calculations trace this phenomenon to transient decoupling of the molecule from its He shell. Our results open novel opportunities for studying non-equilibrium solute-solvent dynamics and quantum thermalization., Comment: 6+7 pages; 4+1 figures; 1 table

We demonstrate a novel experimental implementation to strongly align molecules at full repetition rates of free-electron lasers. We utilized the available in-house laser system at the coherent x-ray imaging beamline at the Linac Coherent Light Source. Chirped laser pulses, i. e., the direct output from the regenerative amplifier of the Ti:Sa chirped pulse amplification laser system, were used to strongly align 2,5-diiodothiophene molecules in a molecular beam. The alignment laser pulses had pulse energies of a few mJ and a pulse duration of 94 ps. A degree of alignment of $\left<\cos^2\!\theta_{2D}\right>$ = 0.85 was measured, limited by the intrinsic temperature of the molecular beam rather than by the available laser system. With the general availability of synchronized chirped-pulse-amplified near-infrared laser systems at short-wavelength laser facilities, our approach allows for the universal preparation of molecules tightly fixed in space for experiments with x-ray pulses., Comment: 10 pages, 5 figures

We give a detailed account of the theoretical analysis and the experimental results of an x-ray-diffraction experiment on quantum-state selected and strongly laser-aligned gas-phase ensembles of the prototypical large asymmetric rotor molecule 2,5-diiodobenzonitrile, performed at the Linac Coherent Light Source [Phys. Rev. Lett. 112, 083002 (2014)]. This experiment is the first step toward coherent diffractive imaging of structures and structural dynamics of isolated molecules at atomic resolution, i. e., picometers and femtoseconds, using x-ray free-electron lasers., Comment: submitted to Faraday Discussions 171 "Emerging Photon Technologies for Chemical Dynamics"

The mixed-field orientation of an asymmetric-rotor molecule with its permanent dipole moment non-parallel to the principal axes of polarizability is investigated experimentally and theoretically. We find that for the typical case of a strong, nonresonant laser field and a weak static electric field complete 3D orientation is induced if the laser field is elliptically polarized and if its major and minor polarization axes are not parallel to the static field. For a linearly polarized laser field solely the dipole moment component along the most polarizable axis of the molecule is relevant resulting in 1D orientation even when the laser polarization and the static field are non parallel. Simulations show that the dipole moment component perpendicular to the most-polarizable axis becomes relevant in a strong dc electric field combined with the laser field. This offers an alternative approach to 3D orientation by combining a linearly-polarized laser field and a strong dc electric field arranged at an angle equal to the angle between the most polarizable axis of the molecule and its permanent dipole moment., Comment: 9 pages, 7 figures, Updated Title and Abstract meta data

We report experimental results on x-ray diffraction of quantum-state-selected and strongly aligned ensembles of the prototypical asymmetric rotor molecule 2,5-diiodobenzonitrile using the Linac Coherent Light Source. The experiments demonstrate first steps toward a new approach to diffractive imaging of distinct structures of individual, isolated gas-phase molecules. We confirm several key ingredients of single molecule diffraction experiments: the abilities to detect and count individual scattered x-ray photons in single shot diffraction data, to deliver state-selected, e. g., structural-isomer-selected, ensembles of molecules to the x-ray interaction volume, and to strongly align the scattering molecules. Our approach, using ultrashort x-ray pulses, is suitable to study ultrafast dynamics of isolated molecules., Comment: submitted to PRL

We show that a 450 fs nonresonant, moderately intense, linearly polarized laser pulse can induce field-free molecular axis alignment of methyliodide molecules dissolved in a helium nanodroplet. Time-resolved measurements reveal rotational dynamics much slower than that of isolated molecules and, surprisingly, complete absence of the sharp transient alignment recurrences characteristic of gas phase molecules. Our results presage a range of new opportunities for exploring both molecular dynamics in a dissipative environment and the properties of He nanodroplets., Comment: 5 pages, 4 figures

We have experimentally and theoretically investigated the mixed-field orientation of rotational-state-selected OCS molecules and we achieve strong degrees of alignment and orientation. The applied moderately intense nanosecond laser pulses are long enough to adiabatically align molecules. However, in combination with a weak dc electric field, the same laser pulses result in nonadiabatic dynamics in the mixed-field orientation. These observations are fully explained by calculations employing, both, adiabatic and non-adiabatic time-dependent models., Comment: 5 pages, 4 figures

We study how the combination of long and short laser pulses, can be used to induce torsion in an axially chiral biphenyl derivative (3,5-difluoro-3',5'-dibromo-4'-cyanobiphenyl). A long, with respect to the molecular rotational periods, elliptically polarized laser pulse produces 3D alignment of the molecules, and a linearly polarized short pulse initiates torsion about the stereogenic axis. The torsional motion is monitored in real-time by measuring the dihedral angle using femtosecond time-resolved Coulomb explosion imaging. Within the first 4 picoseconds, torsion occurs with a period of 1.25 picoseconds and an amplitude of 3 degrees in excellent agreement with theoretical calculations. At larger times the quantum states of the molecules describing the torsional motion dephase and an almost isotropic distribution of the dihedral angle is measured. We demonstrate an original application of covariance analysis of two-dimensional ion images to reveal strong correlations between specific ejected ionic fragments from Coulomb explosion. This technique strengthens our interpretation of the experimental data., Comment: 11 pages, 9 figures

The yield of strong-field ionization, by a linearly polarized probe pulse, is studied experimentally and theoretically, as a function of the relative orientation between the laser field and the molecule. Experimentally, carbonyl sulfide, benzonitrile and naphthalene molecules are aligned in one or three dimensions before being singly ionized by a 30 fs laser pulse centered at 800 nm. Theoretically, we address the behaviour of these three molecules. We consider the degree of alignment and orientation and model the angular dependence of the total ionization yield by molecular tunneling theory accounting for the Stark shift of the energy level of the ionizing orbital. For naphthalene and benzonitrile the orientational dependence of the ionization yield agrees well with the calculated results, in particular the observation that ionization is maximized when the probe laser is polarized along the most polarizable axis. For OCS the observation of maximum ionization yield when the probe is perpendicular to the internuclear axis contrasts the theoretical results., Comment: 14 pages, 4 figures

We make use of an inhomogeneous electrostatic dipole field to impart a quantum-state-dependent deflection to a pulsed beam of OCS molecules, and show that those molecules residing in the absolute ground state, $X ^1\Sigma^+$, $\ket{00^00}$, J=0, can be separated out by selecting the most deflected part of the molecular beam. Past the deflector, we irradiate the molecular beam by a linearly polarized pulsed nonresonant laser beam that impulsively aligns the OCS molecules. Their alignment, monitored via velocity-map imaging, is measured as a function of time, and the time dependence of the alignment is used to determine the quantum state composition of the beam. We find significant enhancements of the alignment (\costhetasqtd $= 0.84$) and of state purity ($> 92$%) for a state-selected, deflected beam compared with an undeflected beam.

The manipulation of the motion of neutral molecules with electric or magnetic fields has seen tremendous progress over the last decade. Recently, these techniques have been extended to the manipulation of large and complex molecules. In this article we introduce experimental approaches to the manipulation of large molecules, i.e., the deflection, focusing and deceleration using electric fields. We detail how these methods can be exploited to spatially separate quantum states and how to select individual conformers of complex molecules. We briefly describe mixed-field orientation experiments made possible by the quantum-state selection. Moreover, we provide an outlook on ultrafast diffraction experiments using these highly controlled samples., Comment: 12 pages, 10 figures

We present combined experimental and theoretical results on strong-field ionization of oriented carbonyl-sulphide molecules by circularly-polarized laser pulses. The obtained molecular frame photoelectron angular distributions show pronounced asymmetries perpendicular to the direction of the molecular electric dipole moment. These findings are explained by a tunneling model invoking the laser-induced Stark shifts associated with the dipoles and polarizabilities of the molecule and its unrelaxed cation. The focus of the present article is to understand the strong-field ionization of one-dimensionally-oriented polar molecules, in particular asymmetries in the emission direction of the photoelectrons. In the following article (Phys. Rev. A 83, 023406 (2011)) the focus is to understand strong-field ionization from three-dimensionally-oriented asymmetric top molecules, in particular the suppression of electron emission in nodal planes of molecular orbitals., Comment: 13 pages, 10 figures

We present a combined experimental and theoretical study on strong-field ionization of a three-dimensionally oriented asymmetric top molecule, benzonitrile (C$_7$H$_5$N), by circularly polarized, nonresonant femtosecond laser pulses. Prior to the interaction with the strong field, the molecules are quantum-state selected using a deflector, and 3-dimensionally (3D) aligned and oriented adiabatically using an elliptically polarized laser pulse in combination with a static electric field. A characteristic splitting in the molecular frame photoelectron momentum distribution reveals the position of the nodal planes of the molecular orbitals from which ionization occurs. The experimental results are supported by a theoretical tunneling model that includes and quantifies the splitting in the momentum distribution. The focus of the present article is to understand strong-field ionization from 3D-oriented asymmetric top molecules, in particular the suppression of electron emission in nodal planes of molecular orbitals. In the preceding article [Dimitrovski et al., Phys. Rev. A 83, 023405 (2011)] the focus is to understand the strong-field ionization of one-dimensionally-oriented polar molecules, in particular asymmetries in the emission direction of the photoelectrons., Comment: 12 pages, 9 figures

The combination of photoelectron spectroscopy and ultrafast light sources is on track to set new standards for detailed interrogation of dynamics and reactivity of molecules. A crucial prerequisite for further progress is the ability to not only detect the electron kinetic energy, as done in traditional photoelectron spectroscopy, but also the photoelectron angular distributions (PADs) in the molecular frame. Here carbonylsulfide (OCS) and benzonitrile molecules, fixed in space by combined laser and electrostatic fields, are ionized with intense, circularly polarized, 30 femtosecond laser pulses. For 1-dimensionally oriented OCS the molecular frame PADs exhibit pronounced anisotropies, perpendicular to the fixed permanent dipole moment, that are absent in PADs from randomly oriented molecules. For 3-dimensionally oriented benzonitrile additional striking structures appear due to suppression of electron emission in nodal planes of the fixed electronic orbitals. Our theoretical analysis, relying on tunneling ionization theory, shows that the PADs reflect nodal planes, permanent dipole moments and polarizabilities of both the neutral molecule and its cation. The calculated results are exponentially sensitive to changes in these molecular properties thereby pointing to exciting opportunities for time-resolved probing of valence electrons dynamics by intense circularly polarized pulses. Molecular frame PADs from oriented molecules will prove important in other contexts notably in emerging free-electron-laser studies where localized inner shell electrons are knocked off by x-ray pulses.

A strong inhomogeneous static electric field is used to spatially disperse a rotationally cold supersonic beam of 2,6-difluoroiodobenzene molecules according to their rotational quantum state. The molecules in the lowest lying rotational states are selected and used as targets for 3-dimensional alignment and orientation. The alignment is induced in the adiabatic regime with an elliptically polarized, intense laser pulse and the orientation is induced by the combined action of the laser pulse and a weak static electric field. We show that the degree of 3-dimensional alignment and orientation is strongly enhanced when rotationally state-selected molecules, rather than molecules in the original molecular beam, are used as targets., Comment: 8 pages, 7 figures; v2: minor updates

Supersonic beams of polar molecules are deflected using inhomogeneous electric fields. The quantum-state selectivity of the deflection is used to spatially separate molecules according to their quantum state. A detailed analysis of the deflection and the obtained quantum-state selection is presented. The rotational temperatures of the molecular beams are determined from the spatial beam profiles and are all approximately 1 K. Unprecedented degrees of laser-induced alignment $(<\cos^2\theta_{2D}>=0.972)$ and orientation of iodobenzene molecules are demonstrated when the state-selected samples are used. Such state-selected and oriented molecules provide unique possibilities for many novel experiments in chemistry and physics., Comment: minor changes, references updated

A strong inhomogeneous static electric field is used to spatially disperse a supersonic beam of polar molecules, according to their quantum state. We show that the molecules residing in the lowest-lying rotational states can be selected and used as targets for further experiments. As an illustration, we demonstrate an unprecedented degree of laser-induced 1D alignment $(<\cos^2\theta_{2D}>=0.97)$ and strong orientation of state-selected iodobenzene molecules. This method should enable experiments on pure samples of polar molecules in their rotational ground state, offering new opportunities in molecular science.