Rotational Dynamics of Quantum State-Selected Symmetric-Top Molecules in Nonresonant Femtosecond Laser Fields.

Rotational dynamics of quantum state selected and unselected CH3I molecules in intense femtosecond laser fields has been studied. The orientation and alignment evolutions are derived from a pump-probe measurement and in good agreement with the numerical results from the time-dependent Schrödinger equation (TDSE) calculation. The different rotational transitions through nonresonant Raman process have been assigned from the Fourier analysis of the orientation and alignment revivals. These revivals are derived from a pump-probe measurement and in good agreement with the numerical results from the TDSE calculation. For the molecules in rotational state |1, ±1, ∓1⟩, the transitions can be assigned to ΔJ = ±1, ±2, while for thermally populated molecules, the transitions are ΔJ = ±2. Our results illustrate that the orientation and alignment revivals of the rotational quantum-state-selected molecules give a deep insight into the rotational excitation pathways for the transition of different rotational states of molecules in ultrafast laser fields.

Charging-induced asymmetric spin distribution in an asymmetric (9,0) carbon nanotube.

Asymmetry in the electronic structure of low-dimensional carbon nanomaterials is important for designing molecular devices for functions such as directional transport and magnetic switching. In this paper, we use density functional theory to achieve an asymmetric spin distribution in a typical (9,0) carbon nanotube (CNT) by capping the CNT with a fullerene hemisphere at one end and saturating the dangling bonds with hydrogen atoms at the other end. The asymmetric structure facilitates obvious asymmetry in the spin distribution along the tube axis direction, with the maximum difference between the ends reaching 1.6 e Å(-1). More interestingly, the heterogeneity of the spin distribution can be controlled by charging the system. Increasing or decreasing the charge by 2e can reduce the maximum difference in the linear spin density along the tube axis to approximately 0.68 e Å(-1) without changing the proportion of the total electron distribution. Further analyses of the electron density difference and the density of states reveal the loss and gain of charge and the participation of atomic orbitals at both ends. Our study characterizes the asymmetric spin distribution in a typical asymmetric carbon system and its correlation with charge at the atomic level. The results provide a strategy for controlling the spin distribution for functional molecular devices through a simple charge adjustment.

Laser induced alignment of state-selected CH3I.

Hexapole state selection is used to prepare CH3I molecules in the |JKM〉 = |1±1∓1〉 state. The molecules are aligned in a strong 800 nm laser field, which is linearly polarised perpendicular to the weak static extraction field E of the time of flight setup. The molecules are subsequently ionised by a second time delayed probe laser pulse. It will be shown that in this geometry at high enough laser intensities the Newton sphere has sufficient symmetry to apply the inverse Abel transformation to reconstruct the three dimensional distribution from the projected ion image. The laser induced controllable alignment was found to have the upper and lower extreme values of 〈P2(cos θ)〉 = 0.7 for the aligned molecule and -0.1 for the anti-aligned molecule, coupled to 〈P4(cos θ)〉 between 0.3 and 0.0. The method to extract the alignment parameters 〈P2(cos θ)〉 and 〈P4(cos θ)〉 directly from the velocity map ion images will be discussed.

The reaction microscope: imaging and pulse shaping control in photodynamics.

Herein, we review the current capabilities and potential of advanced single-particle imaging techniques to study photodynamics in isolated molecules. These reaction microscopes are able to measure the full three-dimensional energy and angular distribution of (correlated) particles such as electrons and molecular fragments ejected after photoexcitation of molecules. In particular, we discuss the performance and capabilities of a novel photoelectron-photoion coincidence imaging spectrometer constructed at LaserLaB Amsterdam. This microscope was developed for the study of nonadiabatic effects in ultrafast time-resolved experiments. It is specifically targeted at optimal control studies of photodynamics to foster and advance our understanding of mechanisms in optimal control with shaped ultrafast laser pulses. We review a few recent experimental results illustrating the wealth of detailed information that can be obtained in such imaging experiments about the interplay between (shaped) laser fields, molecular dynamics, ionization processes and competing multichannel pathways. Furthermore, the recently developed photoelectron-circular-dichroism imaging technique to detect enantiomers and to study chirality effects will be discussed, as a further illustration of the potential of modern reaction microscopes in stereochemistry.

Imaging the rotationally state-selected NO(A,n) product from the predissociation of the A state of the NO-Ar van der Waals cluster.

The origin of the resonant structures in the spectrum of the predissociative part of the A state in the NO-Ar van der Waals cluster has been investigated. We have employed direct excitation to the predissociative part of the NO-Ar A state followed by rotational state selective ionization of the NO fragment. Velocity map imaging of the NO ion yields the recoil energy of the rotational state-selected fragment. A substantial contribution of rotational hotbands to the resonant structures is observed. Our data indicate that a centrifugal barrier as the origin of these resonances can be ruled out. We hypothesize that after the NO-Ar cluster is excited to the A state sufficient mixing within the rotating cluster takes place as it changes geometry from being T shaped in the NO(X)-Ar state to linear in the NO(A)-Ar state. This mixing allows the low energy and high angular momentum (J approximately = 4.5) tumbling motion of the initially populated hotbands in the ground state NO(X)-Ar complex to be converted into NO(A,n = 2) spinning rotation in the A state of the complex. The electronically excited spinning complex falls apart adiabatically producing rotationally excited NO(A,n = 2) at the energetic threshold. This interpretation indicates that the resonances can be attributed to some type of vibrational Feshbach resonance. The appearance energy for the formation of NO(A,n = 0)+Ar is found to be 44294.3+/-1.4 cm(-1).

A photoelectron-photoion coincidence imaging apparatus for femtosecond time-resolved molecular dynamics with electron time-of-flight resolution of sigma=18 ps and energy resolution Delta E/E=3.5%.

We report on the construction and performance of a novel photoelectron-photoion coincidence machine in our laboratory in Amsterdam to measure the full three-dimensional momentum distribution of correlated electrons and ions in femtosecond time-resolved molecular beam experiments. We implemented sets of open electron and ion lenses to time stretch and velocity map the charged particles. Time switched voltages are operated on the particle lenses to enable optimal electric field strengths for velocity map focusing conditions of electrons and ions separately. The position and time sensitive detectors employ microchannel plates (MCPs) in front of delay line detectors. A special effort was made to obtain the time-of-flight (TOF) of the electrons at high temporal resolution using small pore (5 microm) MCPs and implementing fast timing electronics. We measured the TOF distribution of the electrons under our typical coincidence field strengths with a temporal resolution down to sigma=18 ps. We observed that our electron coincidence detector has a timing resolution better than sigma=16 ps, which is mainly determined by the residual transit time spread of the MCPs. The typical electron energy resolution appears to be nearly laser bandwidth limited with a relative resolution of DeltaE(FWHM)/E=3.5% for electrons with kinetic energy near 2 eV. The mass resolution of the ion detector for ions measured in coincidence with electrons is about Deltam(FWHM)/m=14150. The velocity map focusing of our extended source volume of particles, due to the overlap of the molecular beam with the laser beams, results in a parent ion spot on our detector focused down to sigma=115 microm.

Imaging of ultrafast molecular elimination reactions.

Ultrafast molecular elimination reactions are studied using the velocity map ion imaging technique in combination with femtosecond pump-probe laser excitation. A pump laser is used to initiate the dissociative reaction, and after a predetermined time delay a probe laser "interrogates" the molecular system. Ionic fragments are detected with a two-dimensional velocity map imaging detector providing detailed information about the energetic and vectorial properties of mass selected photofragments. In this paper we discuss the ultrafast elimination of molecular iodine, I(2), from IF(2)C-CF(2)I, where the iodine atoms originate from neighboring carbon atoms. By varying the femtosecond delay between pump and probe pulse, it is found that elimination of molecular iodine is a concerted process, although the two carbon-iodine bonds are not broken synchronously. Energetic considerations suggest that the crucial step in this fragmentation process is an electron transfer between the two iodine atoms in the parent molecule, which leads to Coulombic attraction and the creation of an ion-pair state in the molecular iodine fragment.

Vibrational sum frequency scattering from a submicron suspension.

A novel application of vibrational sum frequency generation (VSFG) is developed to study the molecular properties of the surface of submicron particles in suspension. The Rayleigh-Gans-Debye scattering theory is extended to extract the local molecular response from the macroscopic nonlinearly scattered spectral intensity. These results demonstrate the use of VSFG to investigate quantitatively the surface molecular properties of submicron particles, dispersed in solution. It provides information on the order and density of alkane chains and allows us to determine the elements of the local second-order surface susceptibility.