Jochen Küpper

Laser-Induced Alignment and Orientation of Quantum-State-Selected Large Molecules

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 one-dimensional 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.

Photoelectron angular distributions from strong-field ionization of oriented molecules

An experimental study shows how a polar molecule can be oriented in three dimensions by using a combination of laser and electrostatic fields. The approach should help to obtain molecular-frame information about strong-field ionization processes in molecules for which the orientation cannot be determined after ionization.

X-Ray Diffraction from Isolated and Strongly Aligned Gas-Phase Molecules with a Free-Electron Laser

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.

Quantum-state selection, alignment, and orientation of large molecules using static electric and laser fields

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 (=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.

Imaging charge transfer in iodomethane upon x-ray photoabsorption

Tightly tracking charge migration Electron transfer dynamics underlie many chemical and biochemical reactions. Erk et al. examined the charge migration between individual carbon and iodine atoms during dissociation of iodomethane (ICH3) molecules (see the Perspective by Pratt). After initiating scission of the C-I bond with a relatively low-energy laser pulse, they introduced a higher-energy x-ray pulse to instigate ionization and charge migration. Delaying the arrival time of the x-ray pulse effectively varied the separation distance being probed as the fragments steadily drifted apart. The experimental approach should also prove useful for future studies of charge transfer dynamics in different molecular or solid-state systems. Science, this issue p. 288; see also p. 267 A free-electron laser enables precise tracking of electron movement between segments of a dissociating molecule. [Also see Perspective by Pratt] Studies of charge transfer are often hampered by difficulties in determining the charge localization at a given time. Here, we used ultrashort x-ray free-electron laser pulses to image charge rearrangement dynamics within gas-phase iodomethane molecules during dissociation induced by a synchronized near-infrared (NIR) laser pulse. Inner-shell photoionization creates positive charge, which is initially localized on the iodine atom. We map the electron transfer between the methyl and iodine fragments as a function of their interatomic separation set by the NIR–x-ray delay. We observe signatures of electron transfer for distances up to 20 angstroms and show that a realistic estimate of its effective spatial range can be obtained from a classical over-the-barrier model. The presented technique is applicable for spatiotemporal imaging of charge transfer dynamics in a wide range of molecular systems.

The structure of phenol in the S1-state determined by high resolution UV-spectroscopy

Abstract The structure of phenol in the electronically excited S1-state has been examined by rotationally resolved UV-spectroscopy of different isotopomers of phenol. The geometry has been fit to the inertial parameters of 12 isotopomers, using different pseudo-Kraitchman fitting strategies. The resulting r0, rs, rm(1), and rm(2) structures, which differ in the amount of consideration of vibrational effects, will be compared among one another as well as to the results of published ab initio studies. The geometry of the -COH substructure has been determined separately for both electronic states by applying Kraitchman’s equations. Independent of the fitting strategy we found a shortening of the CO bond, an increase of the OH bond length and an expansion of the aromatic ring upon electronic excitation. The internal rotation of the hydroxy group causes line splittings that could be observed in the case of the OH species, but remained unresolved for all OD isotopomers. The S1-state lifetimes of the different isotopomers are shown to depend mainly on the presence of the OH function and depend less on the exchange of CH by CD. Thus, the OH stretching mode is most likely the dominant accepting mode, responsible for the rapid internal conversion in phenol.

Determination of the structures and barriers to hindered internal rotation of the phenol–methanol cluster in the S0 and S1 states

Abstract The rotationally resolved S 1 ←S 0 electronic spectrum of the hydrogen-bonded phenol–methanol cluster has been analyzed. Due to the internal rotation of the methyl group in the methanol moiety, the spectrum of the electronic origin of phenol–methanol is split into A and E subtorsional bands. From a perturbation analysis of the torsional–rotational structure of the electronic origin, the threefold barriers to internal rotation of the methyl group could be determined to be 170 cm −1 in the S 0 state and 150 cm −1 in the S 1 state. The perturbation analysis yielded the angle between the internal rotor axis and the inertial axes of the cluster, which allows the determination of the geometry of the hydrogen bond in both electronic states.

Selector for Structural Isomers of Neutral Molecules

We have selected and spatially separated the two conformers of 3-aminophenol (C(6)H(7)NO) present in a molecular beam. Analogous to the separation of ions based on their mass-to-charge ratios in a quadrupole mass filter, the neutral conformers are separated based on their different mass-to-dipole-moment ratios in an ac electric quadrupole selector. For a given ac frequency, the individual conformers experience different focusing forces, resulting in different transmissions through the selector. These experiments demonstrate that conformer-selected samples of large molecules can be prepared, offering new possibilities for the study of gas-phase biomolecules.

Vibronic coupling in indole: I. Theoretical description of the ¹La-¹Lb interaction and the electronic spectrum

The properties of the three lowest singlet electronic states (ground, (1)L(b), and (1)L(a) states) of indole (C(8)H(7)N) have been calculated with second-order approximate coupled-cluster theory (CC2) within the resolution-of-the-identity approximation. Refined electronic energies at the CC2 optimized structures and transition dipole moments were calculated using a density functional theory multi-reference configuration-interaction (DFT/MRCI) approach. Structures, energies, and dipole moments are reported for all three states and compared to experimental values. From the optimized structures and calculated transition dipole moments, we predict that pure (1)L(b) bands will have positive signs for both the axis reorientation angle theta(T) and the angle theta of the transition dipole moment with respect to the inertial a axis. For (1)L(a) bands the signs of both angles will be reversed. Vibronically coupled bands can exhibit opposite signs for theta and theta(T). The absorption and emission spectra of indole are calculated based on the Franck-Condon Herzberg-Teller approximation using numerical transition dipole moment derivatives at the DFT/MRCI level of theory. Implications for the experimentally observed vibronic spectra are discussed. Predictions are made for rotationally resolved spectra of various rovibronic bands. A conical intersection, connecting the (1)L(b) and (1)L(a) states, which can be accessed to varying extents via different Herzberg-Teller active modes is found approximately 2000 cm(-1) above the (1)L(b) minimum.

Specific Chemical Reactivities of Spatially Separated 3-Aminophenol Conformers with Cold Ca+ Ions

Reactive Conformations Most molecules manifest a fair amount of flexibility at room temperature, in particular through interconversion of rotational conformers—structures that differ by the relative orientation of groups on either side of a single covalent bond. Chang et al. (p. 98; see the Perspective by Heaven) devised a method to explore the comparative reactivities of different conformers. A mixture of the conformers was prepared in a molecular beam cold enough to preclude interconversion; then an electric field was used to push the different conformers apart, spatially resolving subsequent collisional interactions with a target of trapped ions. A molecular beam technique measures the different reactivities of a compound’s distinct rotational conformations. [Also see Perspective by Heaven] Many molecules exhibit multiple rotational isomers (conformers) that interconvert thermally and are difficult to isolate. Consequently, a precise characterization of their role in chemical reactions has proven challenging. We have probed the reactivity of specific conformers by using an experimental technique based on their spatial separation in a molecular beam by electrostatic deflection. The separated conformers react with a target of Coulomb-crystallized ions in a trap. In the reaction of Ca+ with 3-aminophenol, we find a twofold larger rate constant for the cis compared with the trans conformer (differentiated by the O–H bond orientation). This result is explained by conformer-specific differences in the long-range ion-molecule interaction potentials. Our approach demonstrates the possibility of controlling reactivity through selection of conformational states.