Observing the primary steps of ion solvation in helium droplets.

Solvation is a ubiquitous phenomenon in the natural sciences. At the macroscopic level, it is well understood through thermodynamics and chemical reaction kinetics1,2. At the atomic level, the primary steps of solvation are the attraction and binding of individual molecules or atoms of a solvent to molecules or ions of a solute1. These steps have, however, never been observed in real time. Here we instantly create a single sodium ion at the surface of a liquid helium nanodroplet3,4, and measure the number of solvent atoms that successively attach to the ion as a function of time. We found that the binding dynamics of the first five helium atoms is well described by a Poissonian process with a binding rate of 2.0 atoms per picosecond. This rate is consistent with time-dependent density-functional-theory simulations of the solvation process. Furthermore, our measurements enable an estimate of the energy removed from the region around the sodium ion as a function of time, revealing that half of the total solvation energy is dissipated after four picoseconds. Our experimental method opens possibilities for benchmarking theoretical models of ion solvation and for time-resolved measurements of cation-molecule complex formation.

Water is a radiation protection agent for ionised pyrrole.

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(H2O) 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(H2O)+, 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.

Structure determination of alkali trimers on helium nanodroplets through laser-induced Coulomb explosion.

Alkali trimers, Ak3, 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 threefold covariance analysis of the emission direction of the fragment ions and their kinetic energy distributions P(Ekin), we find that Na3, K3, and Rb3 have an equilateral triangular structure, corresponding to that of the lowest lying quartet state A2'4, and determine the equilibrium bond distance Req(Na3) = 4.65 ± 0.15 Å, Req(K3) = 5.03 ± 0.18 Å, and Req(Rb3) = 5.45 ± 0.22 Å. For K3 and Rb3, these values agree well with existing theoretical calculations, while for Na3, the value is 0.2-0.3 Å larger than the existing theoretical results. The discrepancy is ascribed to a minor internuclear motion of Na3 during the ionization process. In addition, 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 |Ψ(R)|2.

Nonadiabatic Laser-Induced Alignment Dynamics of Molecules on a Surface.

We demonstrate that a sodium dimer, Na_{2}(1^{3}Σ_{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 Schrödinger 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.

Generation of Large Vortex-Free Superfluid Helium Nanodroplets.

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.

Laser-Induced Coulomb Explosion Imaging of Aligned Molecules and Molecular Dimers.

We discuss how Coulomb explosion imaging (CEI), triggered by intense femtosecond laser pulses and combined with laser-induced alignment and covariance analysis of the angular distributions of the recoiling fragment ions, provides new opportunities for imaging the structures of molecules and molecular complexes. First, focusing on gas phase molecules, we show how the periodic torsional motion of halogenated biphenyl molecules can be measured in real time by timed CEI, and how CEI of one-dimensionally aligned difluoroiodobenzene molecules can uniquely identify four structural isomers. Next, focusing on molecular complexes formed inside He nano-droplets, we show that the conformations of noncovalently bound dimers or trimers, aligned in one or three dimensions, can be determined by CEI. Results presented for homodimers of CS2, OCS, and bromobenzene pave the way for femtosecond time-resolved structure imaging of molecules undergoing bimolecular interactions and ultimately chemical reactions.

Quantum-State-Sensitive Detection of Alkali Dimers on Helium Nanodroplets by Laser-Induced Coulomb Explosion.

Rubidium dimers residing on the surface of He nanodroplets are doubly ionized by an intense femtosecond laser pulse leading to fragmentation into a pair of Rb^{+} ions. We show that the kinetic energy of the Rb^{+} fragment ions can be used to identify dimers formed in either the X ^{1}Σ_{g}^{+} ground state or in the lowest-lying triplet state, a ^{3}Σ_{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 Li_{2}, Na_{2}, and K_{2}, and will enable femtosecond time-resolved measurements of their rotational and vibrational dynamics, possibly with atomic structural resolution.

Femtosecond Rotational Dynamics of D_{2} Molecules in Superfluid Helium Nanodroplets.

Rotational dynamics of D_{2} molecules inside helium nanodroplets is induced by a moderately intense femtosecond 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 femtosecond 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 B_{He} of the in-droplet D_{2} molecule, determined by Fourier analysis, is the same as B_{gas} for an isolated D_{2} molecule. Our observations show that the D_{2} molecules inside helium nanodroplets essentially rotate as free D_{2} molecules.

Rotational Coherence Spectroscopy of Molecules in Helium Nanodroplets: Reconciling the Time and the Frequency Domains.

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 nonresonant, 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 Schrödinger 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.

Laser-induced alignment dynamics of gas phase CS2 dimers.

Rotational dynamics of gas phase carbon disulfide (CS2) dimers were induced by a moderately intense, circularly polarized alignment laser pulse and measured as a function of time by Coulomb explosion imaging with an intense fs probe pulse. For the alignment pulse, two different temporal intensity profiles were used: a truncated pulse with a 150 ps turn-on and a 8 ps turn-off, or a 'kick' pulse with a duration of 1.3 ps. For both types of pulse, rich rotational dynamics with characteristic full and fractional revivals were recorded, showing that the intermolecular carbon-carbon axis periodically aligns along the propagation direction of the laser pulses. The truncated pulse gave the strongest alignment, which we rationalize as being due to a flat relative phase between the components in the rotational wave packet generated. Fourier analysis of the alignment dynamics gave well-spaced peaks which were fit to determine the rotational constant, B, and the centrifugal constant, DJ, for the ground state of the dimer. Our results agree with values from high-resolution IR spectroscopy. Numerical simulations of the alignment accurately reproduced the experimental dynamics when the truncated pulse or a low intensity kick pulse was used, but failed to reproduce the dynamics induced by a high intensity kick pulse. We posit that the discrepancy is due to excitation of the intermolecular torsional motion by the kick pulse.

X-ray diffractive imaging of controlled gas-phase molecules: Toward imaging of dynamics in the molecular frame.

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 (λ ≈ 130 pm) provided by the Linac Coherent Light Source. Diffracted photons were recorded on the Cornell-SLAC pixel array 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 be 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.

Atomic-resolution imaging of carbonyl sulfide by laser-induced electron diffraction.

Measurements on the strong-field ionization of carbonyl sulfide molecules by short, intense, 2 µm 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, the bond lengths and molecular geometry were extracted from the experimental differential cross sections to a precision better than ±5 pm and in agreement with the known values.

Alignment and Imaging of the CS_{2} Dimer Inside Helium Nanodroplets.

The carbon disulphide (CS_{2}) dimer is formed inside He nanodroplets and identified using fs laser-induced Coulomb explosion, by observing the CS_{2}^{+} ion recoil velocity. It is then shown that a 160 ps moderately intense laser pulse can align the dimer in advantageous spatial orientations which allow us to determine the cross-shaped structure of the dimer by analysis of the correlations between the emission angles of the nascent CS_{2}^{+} and S^{+} ions, following the explosion process. Our method will enable fs time-resolved structural imaging of weakly bound molecular complexes during conformational isomerization, including formation of exciplexes.

Hyperfine-Structure-Induced Depolarization of Impulsively Aligned I_{2} Molecules.

A moderately intense 450 fs laser pulse is used to create rotational wave packets in gas phase 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 nonperiodic 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.

Femtosecond laser induced Coulomb explosion imaging of aligned OCS oligomers inside helium nanodroplets.

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 the corresponding covariance maps reveal the presence of a barrel-shaped structure (as in the gas phase) but also other structures not present in the gas phase, most notably a linear chain structure.

Communication: Switched wave packets with spectrally truncated chirped pulses.

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 ⟨cos2 θ2D⟩, rises along with the pulse intensity and reaches a maximum at the peak of the pulse. After truncation, ⟨cos2 θ2D⟩ drops sharply but exhibits pronounced half and full revivals. The experimental alignment dynamics trace agrees very well with a numerically calculated trace based on the solution of the time-dependent Schrödinger equation. However, the extended periods of field-free alignment of asymmetric tops following pulse truncation reported previously are not reproduced in our work.

Coulomb explosion imaging of CH3I and CH2ClI photodissociation dynamics.

The photodissociation dynamics of CH3I and CH2ClI at 272 nm were investigated by time-resolved Coulomb explosion imaging, with an intense non-resonant 815 nm probe pulse. Fragment ion momenta over a wide m/z range were recorded simultaneously by coupling a velocity map imaging spectrometer with a pixel imaging mass spectrometry camera. For both molecules, delay-dependent pump-probe features were assigned to ultraviolet-induced carbon-iodine bond cleavage followed by Coulomb explosion. Multi-mass imaging also allowed the sequential cleavage of both carbon-halogen bonds in CH2ClI to be investigated. Furthermore, delay-dependent relative fragment momenta of a pair of ions were directly determined using recoil-frame covariance analysis. These results are complementary to conventional velocity map imaging experiments and demonstrate the application of time-resolved Coulomb explosion imaging to photoinduced real-time molecular motion.

Three-Dimensional Molecular Alignment Inside Helium Nanodroplets.

We demonstrate 3D spatial alignment of 3,5-dichloroiodobenzene molecules embedded in helium nanodroplets using nonresonant elliptically polarized 160 ps laser pulses at a 1 kHz repetition rate. Through Coulomb explosion imaging and ion-ion covariance mapping, the 3D alignment is characterized and found to be stronger than that of isolated molecules. The 3D alignment follows the intensity profile of the alignment laser pulse almost adiabatically, except for a delayed response in the helium droplets, which could be exploited for field-free 3D alignment. Our results pave the way for next-generation molecular dynamics and diffraction experiments, performed within a cold helium solvent.

Laser-Induced Rotation of Iodine Molecules in Helium Nanodroplets: Revivals and Breaking Free.

Rotation of molecules embedded in helium 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 helium shell. Our results open novel opportunities for studying nonequilibrium solute-solvent dynamics and quantum thermalization.

Nonadiabatic laser-induced alignment of molecules: Reconstructing ⟨𝖼𝗈𝗌𝟤 θ⟩ directly from ⟨𝖼𝗈𝗌𝟤 θ2D⟩ by Fourier analysis.

We present an efficient, noise-robust method based on Fourier analysis for reconstructing the three-dimensional measure of the alignment degree, ⟨cos2θ⟩, directly from its two-dimensional counterpart, ⟨cos2θ2D⟩. The method applies to nonadiabatic alignment of linear molecules induced by a linearly polarized, nonresonant laser pulse. Our theoretical analysis shows that the Fourier transform of the time-dependent ⟨cos2θ2D⟩ trace over one molecular rotational period contains additional frequency components compared to the Fourier transform of ⟨cos2θ⟩. These additional frequency components can be identified and removed from the Fourier spectrum of ⟨cos2θ2D⟩. By rescaling of the remaining frequency components, the Fourier spectrum of ⟨cos2θ⟩ is obtained and, finally, ⟨cos2θ⟩ is reconstructed through inverse Fourier transformation. The method allows the reconstruction of the ⟨cos2θ⟩ trace from a measured ⟨cos2θ2D⟩ trace, which is the typical observable of many experiments, and thereby provides direct comparison to calculated ⟨cos2θ⟩ traces, which is the commonly used alignment metric in theoretical descriptions. We illustrate our method by applying it to the measurement of nonadiabatic alignment of I2 molecules. In addition, we present an efficient algorithm for calculating the matrix elements of cos2θ2D and any other observable in the symmetric top basis. These matrix elements are required in the rescaling step, and they allow for highly efficient numerical calculation of ⟨cos2θ2D⟩ and ⟨cos2θ⟩ in general.