Phase control over decaying molecular states in intense laser pulses

A time-dependent approach to study phase control over molecular photoabsorption, provided by intense laser pulses, is elaborate. The method allows for the decay linewidth of molecular states and frequency bandwidth of the controlling laser field, and can be applied in weak and strong laser fields where the perturbation theory is invalid. It is shown that a frequency mismatch between the fundamental laser wave and its third harmonic can destroy control. For the example of the one-photon versus three-photon control a simple picture of interference from two monochromatic absorption pathways is not enough to explain phase control and one needs to consider a nonlinear temporal interference of multiquantum transitions. In the perturbation-theory limit an elegant generalization of the famous Shapiro-Hepburn-Brumer equation for the one-photon versus three-photon control is derived. Various numerical calculations illustrate the dependence of phase control on molecular linewidth, fundamental laser wavelength, pulse duration, and peak intensity. It is obtained, that the one-photon versus three-photon control is productive if the molecular state populations, individually produced by each laser wave, have beats of approximately the same frequency. The calculations demonstrate that an enough intense optical pulse can suppress molecular decay and may be used in order to keep stable the state population of a decaying molecule for a long time. The available experimental results for the one-photon versus three-photon control over simple and large polyatomic molecules are analyzed and recommendations for the experimental improvement of control are formulated.     

Field-induced alignment of oxygen and nitrogen by intense femtosecond laser pulses

Field-induced alignment of O2 and N2 was experimentally studied with laser intensities varying from 10(13) to 10(15) W/cm2. When the laser intensity was below the ionization threshold for these molecules, the interaction between the induced dipole moment of molecules and the laser electric field aligned the molecules along the laser polarization direction. After extinction of the exciting laser, the transient alignment revived periodically. Thus macroscopic ensembles of highly aligned O2 and N2 molecules were obtained under field-free conditions. When the laser intensity exceeded the ionization threshold for these molecules, multielectron ionization and Coulomb explosion occurred. Using two linearly polarized laser pulses with crossed polarization, we demonstrated that the rising edge of the laser pulse aligned the molecules along the laser polarization direction prior to ionization, which resulted in strong anisotropic angular distributions of exploding fragments. These results suggest that the degree of alignment should be taken into account when qualitatively comparing the ion yield of these molecules with their companion atoms.     

Explosive desorption and fragmentation of molecular ion from solid fullerene by intense nonresonant femtosecond laser pulses

Desorption of C 60 (+) and its dimer cation was investigated on irradiation with nonresonant femtosecond laser pulses at 1.4 mum. Ionization of solid C 60 revealed strikingly different features, such as the absence of multiply charged molecular ions, the emission of C (+) at low laser intensity, C 2 attachments, delayed ionization, and dimer cation formation, as compared with the gas phase experiments. The large kinetic energy distribution of ions found in this study indicated that the desorption process was mainly driven by an electrostatic mechanism rather than by thermal, photochemical, or volume expansion mechanisms. Singly charged C 60 emission by a Coulomb explosion due to the high density of C 60 (+) is suggested.     

High-order multiphoton fluorescence of organic molecules in solution by intense femtosecond laser pulses

The five and possibly seven-photon fluorescence was observed for organic molecules in solution for the first time. A high-intensity laser enabled us to measure the properties of the high and any-order processes, and the emission could be directly visualized by the eye. These results showed that the common two-photon microscope could be upgraded to the higher order multiphoton microscope by choosing suitable excitation wavelengths. The multiphoton absorption cross sections differed by a factor of 10(33) as the order of the multiphoton process increased.     

The use of intense femtosecond laser pulses for the fragmentation of chitosan

The use of ultrashort laser pulses for the fragmentation of chitosan was investigated. Femtosecond Ti-saphire laser pulses were focused into a flask containing 1.0% chitosan in 0.1 M acetic acid. The effects of the pulse energy (between 0.1 and 0.82 mJ) and the focal length on the laser-induced fragmentation were followed by viscometry and size exclusion chromatography. The chemical structure and degree of acetylation of chitosan and its fragments were studied using elemental analysis, IR and ¹H NMR spectroscopy. The experimental results showed that (i) Ti-saphire laser irradiation induced chain scission in the chitosan macromolecules, (ii) the chemical structure, including the degree of acetylation, did not change significantly upon laser irradiation, (iii) the number of chain scission dependence on laser energy suggests that fragmentation was a two-photon process, and (iv) at constant pulse energy, the molecular weight dropped to a minimum as a function of the focal length (between 45 and 330 mm), indicating that the efficiency of fragmentation was very sensitive to the geometry of the laser beam.     

Control of laser induced molecular fragmentation of n-propyl benzene using chirped femtosecond laser pulses

We present the effect of chirping a femtosecond laser pulse on the fragmentation of n-propyl benzene. An enhancement of an order of magnitude for the relative yields of and in the case of negatively chirped pulses and in the case of positively chirped pulses with respect to the transform-limited pulse indicates that in some fragmentation channel, coherence of the laser field plays an important role. For the relative yield of all other heavier fragment ions, resulting from the interaction of the intense laser field with the molecule, there is no such enhancement effect with the sign of chirp, within experimental errors. The importance of the laser phase is further reinforced through a direct comparison of the fragmentation results with the second harmonic of the chirped laser pulse with identical bandwidth.     

Double ionization and Coulomb explosion of the formic acid dimer by intense near-infrared femtosecond laser pulses

Ionization and fragmentation of formic acid dimers (HCOOH)(2) and (DCOOD)(2) by irradiation of femtosecond laser pulses (100 fs, 800 nm, ~1 × 10(14) W/cm(2)) were investigated by time-of-flight (TOF) mass spectrometry. In the TOF spectra, we observed fragment ions (HCOOH)H(+), (HCOOH)HCOO(+), and H(3)O(+), which were produced via the dissociative ionization of (HCOOH)(2). In addition, we found that the TOF signals of COO(+), HCOO(+), and HCOOH(+) have small but clear side peaks, indicating fragmentation with large kinetic energy release caused by Coulomb explosion. On the basis of the momentum matching among pairs of the side peaks, a Coulomb explosion pathway of the dimer dication, (HCOOH)(2)(2+) → HCOOH(+) + HCOOH(+), was identified with the total kinetic energy release of 3.6 eV. Quantum chemical calculations for energies of (HCOOH)(2)(2+) were also performed, and the kinetic energy release of the metastable dication was estimated to be 3.40 eV, showing good agreement with the observation. COO(+) and HCOO(+) signals with kinetic energies of 1.4 eV were tentatively assigned to be fragment ions through Coulomb explosion occurring after the elimination of a hydrogen atom or molecule from (HCOOH)(2)(2+). The present observation demonstrated that the formic acid dimer could be doubly ionized prior to hydrogen bond breaking by intense femtosecond laser fields.     

Charging of metal clusters in helium droplets exposed to intense femtosecond laser pulses

We review the strong field (10(13)-10(16) W cm(-2)) laser excitation of metal clusters (Cd(N), Ag(N) and Pb(N)) embedded in He nanodroplets. Plasmon enhanced ionization obtained by stretching the laser pulses to several hundreds of femtoseconds or by using dual pulses with a suitable optical delay leads to a Coulomb explosion of highly charged atomic ions. The charging dynamics can be well described by corresponding semiclassical Vlasov simulations. The influence of the He environment on the ionization process and on the final charge distribution is discussed. Evidence is found that He(2+) is generated in collisions with highly charged metal ions. In contrast, singly and doubly charged ions with low recoil energies induce the formation of He snowballs with a distinct shell structure around the ion. Laser intensity thresholds for snowball formation and for the ionization of clusters are investigated by applying intensity selective scanning.     

Efficient and robust strong-field control of population transfer in sensitizer dyes with designed femtosecond laser pulses

We demonstrate control of electronic population transfer in molecules with the help of appropriately shaped femtosecond laser pulses. To this end we investigate two photosensitizer dyes in solution being prepared in the triplet ground state. Excitation within the triplet system is followed by intersystem crossing and the corresponding singlet fluorescence is monitored as a measure of population transfer in the triplet system. We record control landscapes with respect to the fluorescence intensity on both dyes by a systematic variation of laser pulse shapes combining second order and third order dispersion. In the strong-field regime we find highly structured topologies with large areas of maximum or minimum population transfer being insensitive over a certain range of applied laser intensities thus demonstrating robustness. We then compare our experimental results with simulations on generic molecular potentials by solving the time-dependent Schr?dinger equation for excitation with shaped pulses. Control landscapes with respect to population transfer confirm the general trends from experiments. An analysis of regions with maximum or minimum population transfer indicates that coherent processes are responsible for the outcome of our excitation process. The physical mechanisms of joint motion of ground and excited state wave packets or population of a vibrational eigenstate in the excited state permit us to discuss the molecular dynamics in an atom-like picture.     

Optical emission studies of plasma induced by single and double femtosecond laser pulses

Double-pulse femtosecond laser ablation has been shown to lead to significant increase of the intensity and reproducibility of the optical emission signal compared to single-pulse ablation particularly when an appropriate interpulse delay is selected, that is typically in the range of 50–1000 ps. This effect can be especially advantageous in the context of femtosecond laser-induced breakdown spectroscopy analysis of materials. A detailed comparative study of collinear double- over single-pulse femtosecond laser-induced breakdown spectroscopy has been carried out, based on measurements of emission lifetime, temperature and electronic density of plasmas, produced during laser ablation of brass with 450 fs laser pulses at 248 nm. The results obtained show a distinct increase of plasma temperature and electronic density as well as a longer decay time in the double-pulse case. The plasma temperature increase is in agreement with the observed dependence of the emission intensity enhancement on the upper energy level of the corresponding spectral line. Namely, intensity enhancement of emission lines originating from higher lying levels is more profound compared to that of lines arising from lower energy levels. Finally, a substantial decrease of the plasma threshold fluence was observed in the double-pulse arrangement; this enables sensitive analysis with minimal damage on the sample surface.     

Theory of three-dimensional alignment by intense laser pulses

We introduce a theoretical framework for study of three-dimensional alignment by moderately intense laser pulses and discuss it at an elementary level. Several features of formal interest are noted and clarified. Our approach is nonperturbative, treating the laser field within classical and the material system within quantum mechanics. The theory is implemented numerically using a basis set of rotational eigenstates, transforming the time-dependent Schrodinger equation to a set of coupled differential equations where all matrix elements are analytically soluble. The approach was applied over the past few years to explore different adiabatic and nonadiabatic three-dimensional alignment approaches in conjunction with experiments, but its formal details and numerical implementation were not reported in previous studies. Although we provide simple numerical examples to illustrate the content of the equations, our main goal is to complement previous reports through an introductory discussion of the underlying theory.     

Single-active-electron ionization of C60 in intense laser pulses to high charge states

Sequential ionization of the C(60) fullerene to high charge states in ultrashort intense laser pulses is investigated within the strong-field S-matrix approach. Ion yields are calculated and saturation intensities are determined for a broad range of laser wavelengths between 395 and 1800 nm at different pulse lengths. Comparisons of the S-matrix predictions for the saturation intensities with recent experimental data are in an overall satisfactory agreement, indicating that saturation of ionization of this complex molecule can be well described using the single-active-electron approach. The analysis of the results shows that the contributions from the h(u)-highest occupied molecular orbital to the ion yields dominate as compared to those from the inner valence shells h(g) and g(g). Finally, it is demonstrated that the suppression of ionization of C(60) and its ions, as observed in experiments, can be interpreted within the present theory as due to the finite cage size of the fullerenes and a multi-slit-like interference effect between partial waves emitted from the different nuclei of the fullerenes.     

Fragmentation dynamics of methane by few-cycle femtosecond laser pulses

The fragmentation pattern of CH4 was experimentally studied at an intensity of approximately 10(14) W/cm2 with laser durations varying from 8 to 110 fs. When the laser duration was 8 fs, only the primarily fragmental CH3+ ion was observed in addition to the parent CH4+ ion. When the laser duration was 30 fs, small fragmental CH2+ and H+ ions appeared. When the laser duration was 110 fs, some doubly charged ions were also observed in addition to the abundant singly charged ions. The large mass spectra difference demonstrated that the pulse duration had a strong effect on the fragmentation of the parent ion produced in the single ionization. The effect of laser intensity on the fragmentation of CH4+ was also studied for few-cycle femtosecond laser pulses. The results demonstrated that the first-return recollision between the rescattered electron and the parent ion played a significant role in the fragmentation dynamics of the parent ion. Depending on the ion-electron impact energy, the recollision excited the parent ion to a dissociated state or doubly charged state. The experimentally observed singly charged fragmental ions resulted from the recollision-induced dissociation of CH4+ or the Coulomb explosion of CH(4)2+.     

Unveiling the nonadiabatic rotational excitation process in a symmetric-top molecule induced by two intense laser pulses

We experimentally investigate the nonadiabatic rotational excitation process of a symmetric-top molecule, benzene, in the electronic ground state irradiated by intense nonresonant ultrafast laser fields. The initial rotational-state distribution was restricted mostly to the five lowest levels with different nuclear spin modifications by an extensive adiabatic cooling with the rotational temperature well below 1 K, and distributions after the interaction with a femtosecond double-pulse pair (3-5 TW/cm(2) each with 160 fs duration) with time delays were probed in a quantum-state resolved manner by employing resonant enhanced multiphoton ionization via the S(1) ← S(0) 6(0) (1) vibronic transition. Populations of 10 rotational levels with J ranging from 0 to 4 and K from 0 to 3 were examined to show an oscillatory dependence on the time delay between the two pulses. Fourier analysis of the beat signals provides the coupling strengths between the constituent levels of the rotational wave packets created by the nonadiabatic excitation. These data are in good agreement with the results from quantum mechanical calculations, evidencing stepwise excitation pathways in the wave packet creation with ΔJ = 2 in the K = 0 stack while ΔJ = 1 and 2 in the K > 0 stacks.     

Preparation and resolution of molecular states by coherent sequences of phase-locked ultrashort laser pulses

We study the application of nonlinear wave packet interferometry to the preparation and resolution of the overlaps of nonstationary nuclear wave functions evolving in an excited electronic state of a diatomic molecule. It is shown that possible experiments with two phase-locked ultrashort pulsepairs can be used to determine a specific vibrational wave packet state in terms of coherent states of the ground electronic state. We apply this scheme to an idealized molecule with harmonic potential energy surfaces and to the X <-- B transition states of the iodine molecule. Our results indicate that this scheme is very promising as a potential tool to quantum control.     

Mode-focusing in molecules by feedback-controlled shaping of femtosecond laser pulses

The feasibility of mode-selective excitation with broadband femtosecond laser pulses is demonstrated for toluene in liquid phase. A learning-loop optimal control scheme was applied to a stimulated Raman excitation process. Modifications of the phase shape of one of the exciting pulses resulted in dramatic changes of the mode distribution reflected in coherent anti-Stokes Raman spectra. An evolutionary algorithm guided the coherent excitation process to a selective enhancement or suppression of one or more vibrational modes over the complete coherence lifetime spanning several picoseconds. New ways of spectral filtering as well as exciting possibilities of mode-selective studying of chemical reaction dynamics are indicated.     

Dissociative ionization of ethanol by 400 nm femtosecond laser pulses

The dissociative ionization of ethanol in short-pulsed laser fields at approximately 400 nm is investigated. The yield ratio of the C-O bond breaking with respect to the C-C bond breaking increases sharply as the temporal width increases from 60 to 400 fs, and the yield ratio is two to three times as large as that at 800 nm in the entire pulse-width range of 60-580 fs. The enhancement of the C-O bond breaking of singly charged ethanol at 400 nm and the bond elongation prior to the Coulomb explosion of doubly charged ethanol occurring in the relatively weak light field intensity of 10(12)-10(13) W cm(2) is interpreted by the efficient light-induced coupling among the electronic states at the shorter wavelength of 400 nm. From the double pulse experiment, in which ethanol is irradiated with a pair of short pulses (<80 fs), the most efficient coupling occurs at Deltat=160 fs that is much earlier than Deltat=250 at 800 nm, where Deltat denotes the temporal separation of the two pulses, indicating that the nonadiabatic field-induced potential crossings of singly charged ethanol occurs much earlier at 400 nm than at 800 nm.     

Enhancement of anthracene fragmentation by circularly polarized intense femtosecond laser pulse

The authors compared circularly and linearly polarized lights in the ionization and fragmentation of anthracene, using 800 nm femtosecond laser pulses at intensities of 10(13)-10(15) W cm-2. Singly and doubly charged intact molecular ions as well as numerous fragment ions were observed in the mass spectra, which were investigated as a function of laser intensity and polarization. At comparable intensities above the saturation threshold for complete ionization, the fragmentation pathways are enhanced with a circularly polarized field compared to a linearly polarized field. Resonant excitation of the molecular cation through the 2Au<--2Bg transition is proposed to be the initial step to ion fragmentation. The circularly polarized field interacts with a larger fraction of the randomly oriented molecules than the linearly polarized field, and this is considered to be the reason for the enhanced fragmentation brought about by circularly polarized light.     

Dissociative ionization of methane by chirped pulses of intense laser light

Measurements have been made of optical field-induced ionization and fragmentation of methane molecules at laser intensities in the 10(16) W cm(-2) range using near transform limited pulses of 100 fs duration as well as with chirped pulses whose temporal profiles extend up to 1500 fs. Data is taken both in constant-intensity and constant-energy modes. The temporal profile of the chirped laser pulse is found to affect the morphology of the fragmentation pattern that is measured. Besides, the sign of the chirp also affects the yield of fragments like C2+, H+, and H2+ that originate from methane dications that are formed by optical field-induced double ionization.