Time-dependent alignment of molecules trapped in octahedral crystal fields

The hindered rotational states of molecules confined in crystal fields of octahedral symmetry, and their time-dependent alignment obtained by pulsed nonresonant laser fields, are studied computationally. The control over the molecular axis direction is discussed based on the evolution of the rotational wave packet generated in the cubic crystal-field potential. The alignment degree obtained in a cooperative case, where the alignment field is applied in a favorable crystal-field direction, or in a competitive direction, where the crystal field has a saddle point, is presented. The investigation is divided into two time regimes where the pulse duration is either ultrashort, leading to nonadiabatic dynamics, or long with respect to period of molecular libration, which leads to synchronous alignment due to nearly adiabatic following. The results are contrasted to existing gas phase studies. In particular, the irregularity of the crystal-field energies leads to persistent interference patterns in the alignment signals. The use of nonadiabatic alignment for interrogation of crystal-field energetics and the use of adiabatic alignment for directional control of molecular dynamics in solids are proposed as practical applications.     

Stark-selected beam of ground-state OCS molecules characterized by revivals of impulsive alignment

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)Σ(+), |00(0)0>, 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 ( = 0.84) and of state purity (>92%) for a state-selected, deflected beam compared with an undeflected beam.     

A supersonic beam of cold lithium hydride molecules

We have developed a source of cold LiH molecules for Stark deceleration and trapping experiments. Lithium metal is ablated from a solid target into a supersonically expanding carrier gas. The translational, rotational, and vibrational temperatures are 0.9+/-0.1, 5.9+/-0.5, and 468+/-17 K, respectively. Although they have not reached thermal equilibrium with the carrier gas, we estimate that 90% of the LiH molecules are in the ground state, X (1)Sigma(+)(v=0,J=0). With a single 7 ns ablation pulse, the number of molecules in the ground state is 4.5+/-1.8 x 10(7) molecules/sr. A second, delayed, ablation pulse produces another LiH beam in a different part of the same gas pulse, thereby almost doubling the signal. A long pulse, lasting 150 micros, can make the beam up to 15 times more intense.     

Irreversible thermal denaturation of beta-lactoglobulin retards adsorption of carrageenan onto beta-lactoglobulin-coated droplets

The influence of isothermal heat treatments on the adsorption of anionic carrageenan molecules to the surfaces of anionic beta-lactoglobulin-coated droplets has been investigated. The zeta-potential, mean particle diameter, microstructure, and creaming stability of emulsions containing beta-lactoglobulin-coated droplets and/or carrageenan molecules that had previously been heat treated at temperatures ranging from 30 to 90 degrees C for 20 min were measured (pH 6.0, 150 mM NaCl). Three different heat treatments were used to establish the physicochemical origin of the influence of thermal history on the adsorption of carrageenan molecules to the protein coated droplets: (i) droplets and carrageenan were mixed at room temperature, then heated together; (ii) droplets were heated, cooled to room temperature, then mixed with carrageenan; (iii) carrageenan was heated, cooled to room temperature, then mixed with droplets. For treatments i and ii appreciably more carrageenan adsorbed to the protein-coated droplet surfaces at temperatures < or = 60 degrees C than at higher temperatures. For treatment iii, carrageenan adsorbed to the droplet surfaces across the whole temperature range. These results suggest that an irreversible thermal denaturation of the adsorbed beta-lactoglobulin molecules inhibited the adsorption of carrageenan molecules to the droplet surfaces. We postulate that there is a patch of positive charge on the surface of the native globular protein molecules which becomes more diffuse upon thermal denaturation. We found that the carrageenan molecules were unable to protect the beta-lactoglobulin-coated droplets at high temperatures (T > 60 degrees C) because they desorbed from the droplet surfaces. Nevertheless, adsorption of iota-carrageenan was capable of protecting the droplets against flocculation caused by surface denaturation of the adsorbed proteins at lower temperatures (T < or = 50 degrees C).     

Opto-thermal reorientation of nematics with two-fold degenerate alignment

The preferred direction of alignment of the liquid crystal molecules in nematics with two-fold degenerate alignment can be affected substantially by changing the temperature or by applying an electric field. As a result, an almost in-plane switching of the molecules occurs. Here, we report an opto-thermal reorientation effect in a nematic with two-fold degenerate alignment due to a local heating of the liquid crystal by a high power laser beam. The mechanism of this phenomenon is discussed. The opto-thermal reorientation of the molecules makes it possible to visualize the temperature distribution in the illuminated cell and some applications can be foreseen.     

Efficient Coherent Population Transfer of D2 Molecules by Stark-induced Adiabatic Raman Passage

Preparation of a high flux of hydrogen molecules in a specific vibrationally excited state is the major prerequisite and challenge in scattering experiments that use vibrationally excited hydrogen molecules as the target. The widely used scheme of stimulated Raman pumping suffers from coherent population return which severely limits the excitation efficiency. Re-cently we successfully transferred D₂ molecules in the molecular beam from (v=0, J=0) to (v=1, J=0) level, with the scheme of Stark-induced adiabatic Raman passage. As high as 75% of the excitation efficiency was achieved. This excitation technique promise to be a unique tool for crossed beam and beam-surface scattering experiments which aim to reveal the role of vibrational excitation of hydrogen molecules in the chemical reaction.     

Dissipative dynamics of laser induced nonadiabatic molecular alignment

Nonadiabatic alignment induced by short, moderately intense laser pulses in molecules coupled to dissipative environments is studied within a nonperturbative density matrix theory. We focus primarily on exploring and extending a recently proposed approach [Phys. Rev. Lett. 95, 113001 (2005)], wherein nonadiabatic laser alignment is used as a coherence spectroscopy that probes the dissipative properties of the solvent. To that end we apply the method to several molecular collision systems that exhibit sufficiently varied behavior to represent a broad variety of chemical environments. These include molecules in low temperature gas jets, in room temperature gas cells, and in dense liquids. We examine also the possibility of prolonging the duration of the field free (post-pulse) alignment in dissipative media by a proper choice of the system parameters.     

Use of helium nanodroplets for assembly, transport, and surface deposition of large molecular and atomic clusters

The utility of continuous beam of helium droplets for assembly, transport, and surface deposition of metal and molecular clusters is studied. Clusters of propyne having from about 10 to 10(4) molecules were obtained via sequential pickup of molecules by He droplets with average sizes in the range of 10(4)-10(7) atoms. The maximum attainable flux of the propyne molecules carried by He droplets was found to be in the range of (5-15)x10(15) molecules sr(-1) s(-1), being larger in larger droplets. The size of the clusters and the flux of the transported species are ultimately limited by the evaporative extinction of the entire helium droplet upon capture of particles. It is shown that the attenuation of the He droplet beam in the process of the cluster growth can be used in order to obtain the average size and the binding energy of the clusters. Furthermore, we used He droplets for assembling and surface deposition of gold and silver clusters having about 500 atoms. Typical deposition rate of metal atoms of about 3 x 10(15) atoms sr(-1) s(-1) is comparable to or larger than obtained with other beam deposition techniques. We propose that doping of He droplets by Au and Ag atoms in two separate pickup chambers leads to formation of the bimetal clusters having core-shell structure.     

Anisotropic intermolecular potentials for NOAr and NOKr from total differential cross section measurements

Angular distributions of NO scattered off Ar and Kr in the thermal energy range are measured in crossed molecular beam experiments. Information on the anisotropy of the interaction potential is obtained from the damping of the rainbow structure within the framework of the infinite-order-sudden approximation. The derived potential energy surfaces are compared with the results of a previous experimental investigation and with the PES of the related O₂-and N₂-rare gas systems.     

A simulation test of the optical Kerr mechanism for laser-induced nucleation

Recent experiments have demonstrated that intense, nanosecond laser pulses can induce crystal nucleation from supersaturated solutions that are transparent at the incident wavelengths, a phenomenon termed nonphotochemical laser-induced nucleation (NPLIN). Previous work has proposed that this effect is due to the alignment of solute molecules in solution due to the electric field of the applied laser light, promoting crystalline order. We have used simulations of NPLIN to examine how an orientational bias in solution affects nucleation with Monte Carlo simulations of a Potts lattice gas model. We examine this effect within both a classical, one-step nucleation framework as well as in the context of two-step nucleation. Our results indicate that an orientational bias can reduce the free energy barrier to nucleation within the one-step picture as well as promote the crystallization of amorphous precritical nuclei (the rate-determining step in the two-step picture). However, these effects are only present with field strengths that are much greater than those used in experiments.     

Generation and characterization of highly vibrationally excited molecular beam

A simple method to generate and characterize a pure highly vibrationally excited azulene molecular beam is demonstrated. Azulene molecules initially excited to the S4 state by 266-nm UV photons reach high vibrationally excited levels of the ground electronic state upon rapid internal conversion from the S4 electronically excited state. VUV laser beams at 157 and 118 nm, respectively, are used to characterize the relative concentrations of the highly vibrationally excited azulene and the rotationally and vibrationally cooled azulene in the molecular beam. With a laser intensity of 34 mJ/cm2, 75% of azulene molecules absorb a single 266-nm photon and become highly vibrationally excited molecules. The remaining ground-state azulene molecules absorb two or more UV photons, ending up either as molecular cations, which are repelled out of the beam by an electric field, or as dissociation fragments, which veer off the molecular-beam axis. No azulene without absorption of UV photons is left in the molecular beam. The molecular beam that contains only highly vibrationally excited molecules and carrier gas is useful in various experiments related to the studies of highly vibrationally excited molecules.     

NMR at 900 MHz

The very first high-resolution NMR spectra recorded at 900 MHz in July 2000 have demonstrated the benefits of increased magnetic field strength for studies of large biomolecules such as proteins and nucleic acids. Increased sensitivity and resolution for such molecules can only be observed in experiments that are optimized for transverse relaxation (TROSY). Substantial effects of magnetic alignment can easily be observed not only in paramagnetic proteins, but even in small molecules, such as chloroform. Such effects can be very useful for structural studies of biopolymers. The extreme resolution allows studies of very weak interactions in proteins. For instance, long-range H/D isotope effects are easily observed in H-N correlation experiments. The first systematic studies of relaxation properties of N-15 nuclei have been carried out for proteins at 500, 600, 800, and 900 MHz.     

Orientation of dipole molecules and clusters upon adiabatic entry into an external field

The induced polarization of a beam of polar clusters or molecules passing through an electric or magnetic field region differs from the textbook Langevin-Debye susceptibility. This distinction, which is important for the interpretation of deflection and focusing experiments, arises because instead of acquiring thermal equilibrium in the field region, the beam ensemble typically enters the field adiabatically, i.e., with a previously fixed distribution of rotational states. We discuss the orientation of rigid symmetric top systems with a body-fixed electric or magnetic dipole moment. The analytical expression for their "adiabatic-entry" orientation is elucidated and compared with exact numerical results for a range of parameters. The differences between the polarization of thermodynamic and "adiabatic-entry" ensembles of prolate and oblate tops, and of symmetric top and linear rotators, are illustrated and identified.     

Study on polyvinylidene fluoride as alignment layer in twist-nematic liquid crystal display

The material with high dielectric constant can significantly affect the distribution of the electric field, so this kind of material has great potential in liquid crystal display. In this paper, polyvinylidene fluoride (PVDF) as alignment layer in liquid crystal display was analysed. The optical property, mechanical property, thermal stability and electrical property of PVDF were measured. Experiments show that the absorbance of PVDF material is 0.2 (or less) in visible light, which is better than the conventional alignment material polyimide (PI). The alignment effect can be generated by mechanical friction and the liquid crystal molecules are ordered or aligned, and PVDF can maintain good thermal stability as temperature is lower than 400°C. Since the dielectric constant of PVDF is usually between 6.0 and 8.0, it has significant effect on the distribution of the electric field in the liquid crystal display, and its dielectric loss is also less than PI. The lower operating voltage and the faster response time are obtained from the experiment. It can be confirmed by the experiments that PVDF could be used in liquid crystal display (LCD) as the alignment layer to improve LCD’s characteristics.     

Directional states of symmetric-top molecules produced by combined static and radiative electric fields

We show that combined electrostatic and radiative fields can greatly amplify the directional properties, such as axis orientation and alignment, of symmetric top molecules. In our computational study, we consider all four symmetry combinations of the prolate and oblate inertia and polarizability tensors, as well as the collinear and perpendicular (or tilted) geometries of the two fields. In, respectively, the collinear or perpendicular fields, the oblate or prolate polarizability interaction due to the radiative field forces the permanent dipole into alignment with the static field. Two mechanisms are found to be responsible for the amplification of the molecules' orientation, which ensues once the static field is turned on: (a) permanent-dipole coupling of the opposite-parity tunneling doublets created by the oblate polarizability interaction in collinear static and radiative fields and (b) hybridization of the opposite parity states via the polarizability interaction and their coupling by the permanent dipole interaction to the collinear or perpendicular static field. In perpendicular fields, the oblate polarizability interaction, along with the loss of cylindrical symmetry, is found to preclude the wrong-way orientation, causing all states to become high-field seeking with respect to the static field. The adiabatic labels of the states in the tilted fields depend on the adiabatic path taken through the parameter space comprised of the permanent and induced-dipole interaction parameters and the tilt angle between the two field vectors.     

Superfluid helium droplets: a uniquely cold nanomatrix for molecules and molecular complexes

Herein, recent experiments on the spectroscopy and chemical reactions of molecules and complexes embedded in helium droplets are reviewed. In the droplets, a high spectroscopic resolution, which is comparable to the gas phase is achieved, while an isothermal low-temperature environment is maintained by evaporative cooling at T =0.37 K (4He droplets) or 0.15 K (3He droplets), lower than possible in most solid matrices. Thus the helium-droplet technique combines the benefits of both the gas phase and the classical matrix-isolation techniques. Most important, the superfluid helium facilitates binary encounters, and absorbs the released binding energy upon recombination. Thus the droplet can be viewed as an isothermal nanoscopic reactor, which isolates single molecules, clusters, or even a single reactive encounter at ultralow temperatures.     

Postnucleation droplet growth in supersaturated gas with arbitrary vapor concentration

This work concerns the reexamination and extension of the current theory of phase transition dynamics for liquid droplets growing on soluble aerosols from a supersaturated gas mixture for the general case of arbitrary value of vapor concentration. We found that the inconsistency in the common treatment of the vapor diffusion, due to an implicit assumption of the constancy of gas density in the vicinity of a droplet by neglecting its dependency on temperature and vapor concentration, leads to the obvious discrepancy in the Maxwell expression for the growth rate regarding droplets of near critical size. Restoring the correct treatment of the vapor diffusion in terms of the mass concentration of water vapor and taking into the consideration variations of gas density in the vicinity of a droplet in compliance with the equation of state of moist air, we have obtained a new expression for the droplet growth rate valid for an arbitrary value of vapor concentration. The limitations imposed by the molecular kinetic fluxes to postnucleation diffusional growth of small droplets with a large Knudsen number are also reevaluated to include previously neglected physical effects. In particular, the essential contribution of the vapor molecular energy flux into the total kinetic molecular heat flux as well as the temperature variations of mean thermal velocities of air and vapor molecules in the vicinity of the droplet interface have been taken into consideration. Surprisingly significant differences have been found in new expressions derived for the droplet growth rate and droplet temperature, even in the limit of small vapor concentration, if comparing with commonly used results. These findings could help with better interpretation of experimental measurements to infer more reliable data for the mass and thermal accommodations coefficients.     

Field asymmetric waveform ion mobility spectrometry studies of proteins: Dipole alignment in ion mobility spectrometry?

Approaches to separation and characterization of ions based on their mobilities in gases date back to the 1960s. Conventional ion mobility spectrometry (IMS) measures the absolute mobility, and field asymmetric waveform IMS (FAIMS) exploits the difference between mobilities at high and low electric fields. However, in all previous IMS and FAIMS experiments ions experienced an essentially free rotation; thus the separation was based on the orientationally averaged cross-sections Omega(avg) between ions and buffer gas molecules. Virtually all large ions are permanent electric dipoles that will be oriented by a sufficiently strong electric field. Under typical FAIMS conditions this will occur for dipole moments >400 D, found for many macroions including most proteins above approximately 30 kDa. Mobilities of aligned dipoles depend on directional cross-sections Omega(dir) (rather than Omega(avg)), which should have a major effect on FAIMS separation parameters. Here we report the FAIMS behavior of electrospray-ionization-generated ions for 10 proteins up to approximately 70 kDa. Those above 29 kDa exhibit a strong increase of mobility at high field, which is consistent with predicted ion dipole alignment. This effect expands the useful FAIMS separation power by an order of magnitude, allowing separation of up to approximately 10(2) distinct protein conformers and potentially revealing information about Omega(dir) and ion dipole moment that is of utility for structural characterization. Possible approaches to extending dipole alignment to smaller ions are discussed.