ATI of complex systems: Ar and C<Subscript>60</Subscript>

Above threshold ionization of two structurally different systems is presented namely a rare gas such as argon and the more complex C₆₀ fullerene. We show that the ionization dynamics is different and is dominated by the presence of high-lying Rydberg states in Ar and low-lying bound states in C₆₀. The study is based on a theoretical (solving the time dependent Schrödinger equation) and/or experimental (using measurements from a photoelectron imaging spectrometer) aspect.Received: 20 December 2002, Published online: 24 April 2003PACS: 33.80.Rv Multiphoton ionization and excitation to highly excited states (e.g., Rydberg states) - 32.80.Fb Photoionization of atoms and ions - 36.40.-c Atomic and molecular clusters - 33.60.-q Photoelectron spectra - 61.48.+c Fullerenes and fullerene-related materials     

Control of the Coulomb explosion of I<Subscript>2</Subscript>

We present calculated results for the optimization highly-charged fragment ion formation in the Coulomb explosion of I₂ in an intense laser field. Calculations are performed using a simple genetic algorithm and a classical model for the Coulomb explosion process. We find that at low intensity the production of highly-charged fragment ions is optimized by a Fourier-limited pulse, whereas at higher intensity the Coulomb explosion is optimized by a sequence of pulses, with a time-separation determined by enhanced ionization at the critical internuclear distance. Our calculations provide insight into the sensitivity of adaptive pulse shaping experiments to the parameters and evolutionary approaches used.Received: 6 January 2003, Published online: 15 July 2003PACS: 33.80.Rv Multiphoton ionization and excitation to highly excited states (e.g., Rydberg states) - 82.53.Eb Pump probe studies of photodissociation - 02.60.Pn Numerical optimization     

Vibronic structure of the 3s Rydberg state of the 2-methylallyl radical

Resonance-enhanced multiphoton ionization combined with electronic ground state depletion spectroscopy of jet-cooled 2-methylallyl (C₄H₇) radicals provides vibronic spectra of the 3s and 3p Rydberg states. Analysis of the vibronic structure following one-photon and two-photon excitation of rovibronically cold 2-methylallyl radicals and its isotopologues C₄H₄D₃ and C₄D₇ reveals transitions to more than 30 vibrational levels in the 3s Rydberg state that are identified and reassigned on the basis of predictions from ab initio calculations and results from pulsed-field-ionization zero-kinetic-energy photoelectron spectra obtained with resonant multiphoton excitation via selected intermediate states. Depletion spectroscopy reveals transitions to short-lived 3p Rydberg states that have a large oscillator strength.     

Two-photon absorption of high-power picosecond pulses in PbWO<Subscript>4</Subscript>, ZnWO<Subscript>4</Subscript>, PbMoO<Subscript>4</Subscript>, and CaMoO<Subscript>4</Subscript> crystals

The nonlinear process of two-photon interband absorption is studied in tungstate and molybdate oxide crystals excited by a sequence of high-power picosecond pulses with a wavelength of 523.5 nm. The transmission of the crystals is measured for the excitation pulse intensity up to 100 GW/cm². The pulse intensity in the crystals initially transparent at a wavelength of 523.5 nm is strongly limited due to two-photon absorption (TPA), and the reciprocal transmission in PbWO₄ and ZnWO₄ crystals reaches 50–60. In all crystals, TPA induces long-lived one-photon absorption, which affects the nonlinear process dynamics and leads to a hysteresis in the dependence of the transmission on the laser excitation intensity. Absorption dichroism manifests itself in a significant difference in the transmission intensities when the principal orthogonal optical axes of the crystals are excited. The TPA coefficients are determined during the excitation of two optical axes of the crystals. TPA coefficients β for the crystals vary over a wide range, namely, from β = 2.4 cm/GW for PbMoO₄ to β = 0.14 cm/GW for CaMoO₄, and the values of β can differ almost threefold when different optical axes of a crystal are excited. Good agreement is achieved between the measured intensities limited by TPA and the estimates calculated from the measured nonlinear coefficients. Stimulated Raman scattering (SRS) upon excitation at a wavelength of 523.5 nm is only detected in two of the four crystals under study. The experimental results make it possible to explain the suppression of SRS by its competition with TPA, and the measured nonlinear coefficients are used to estimate this suppression.     

Atomic and molecular ions in intense ultra-fast laser fields

The interaction of a 60 fs 790 nm laser pulse with beams of Ar⁺, C⁺, H₂ ⁺, HD⁺ and D₂ ⁺ are discussed. Intensities up to 10¹⁶ Wcm^-2 are employed. An experimental z-scanning technique is used to resolve the intensity dependent processes in the confocal volume.Received: 6 January 2003, Published online: 15 July 2003PACS: 32.80.Fb Photoionization of atoms and ions - 33.80.Rv Multiphoton ionization and excitation to highly excited states (e.g., Rydberg states) - 42.50.Hz Strong-field excitation of optical transitions in quantum systems; multiphoton processes; dynamic Stark shift     

CASPT2 and CCSD(T) calculations of dipole moments and polarizabilities of acetone in excited states

The acetone molecule is investigated in its ground state and valence ^1,3n-π*, ^1,3π-π*, and ^1,3σ-π* excited states and Rydberg ^1,3n-3s, ^1,3π-3?, ^1,3n-3p_y and ^1,3π-3p_y states using the CASSCF, CASPT2, and CCSD(T) methods. Equilibrium geometries of excited states are obtained and their changes with respect to the ground state are discussed. For most excited states the C_2v symmetry of the ground state is lowered to the C_s symmetry. A series of valence vertical and adiabatic excitation energies is presented along with excitation energies for Rydberg states. The main body of the paper contains Finite-Field Perturbation Theory (FFPT) calculations of electric properties of the vertically as well as geometry relaxed excited states. Dipole moments of valence excited states decrease significantly upon excitation, being about one half of the ground state dipole moment. Polarizabilities usually change upon excitation much less (increase by about 30%) but hyperpolarizabilities are enhanced up to one or two orders of magnitude. The orientation of the dipole moment is reversed in some vertically excited Rydberg states. Properties of the ground and excited states are discussed considering alterations of the electronic structure and shifts in the geometry.     

Statics and dynamics of excited states of oxygen-deficient centers in SiO<Subscript>2</Subscript>

The parameters of excited states of oxygen-deficient centers (ODCs) in high-energy-electron irradiated crystalline and glassy SiO₂ have been studied using optical absorption, luminescence, and photoelectron emission spectroscopy. Additional evidence has been gained in support of the model of a neutral oxygen vacancy in ODCs, the diagram of electronic transitions has been refined, and their characteristics have been quantified. The possibility of ionization of the singlet and triplet defect states at a transition to the anomalously relaxed configuration has been demonstrated using the particular example of α-ODCs. Nonradiative excitation transfer from nonbridging oxygen centers to the triplet ODC state has been observed.     

Photodesorption of O<Subscript>2</Subscript> from Ag<Subscript>2</Subscript><Superscript>-</Superscript>: A time-resolved study of Ag<Subscript>2</Subscript>O<Subscript>2</Subscript><Superscript>-</Superscript>

We present time-resolved photoelectron spectra of mass-selected Ag₂O₂ anions. The anions are photoexcited by photons with an energy of 3.1 eV, and photoelectron spectra of the excited species Ag₂O₂ ^{- *} and the subsequently appearing fragments are recorded using a probe laser pulse with a photon energy of 1.5 eV. The excited state of Ag₂O₂ ^- has a short lifetime of 130 fs±70 fs only and decays by direct photodesorption of O₂. The data demonstrate the ability of time-resolved photoelectron spectroscopy (TR-PES) to observe the breaking of chemical bonds if the decay process of the excited state is direct (non-thermal desorption). The data are compared to recent results of a NeNePo experiment [1] on the same system. PACS 68.43.Tj; 78.47.+p; 33.80.Eh; 36.40.-c     

Enhanced nonlinear double excitation of He in intense extreme ultraviolet laser fields

Nonlinear, three-photon double excitation of He in intense extreme ultraviolet free-electron laser fields (～24.1 eV, ～5 TW/cm2) is presented. Resonances to the doubly excited states converging to the He+ N=3 level are revealed by the shot-by-shot photoelectron spectroscopy and identified by theoretical calculations based on the time-dependent Schr?dinger equation for the two-electron atom under a laser field. It is shown that the three-photon double excitation is enhanced by intermediate Rydberg states below the first ionization threshold, giving a greater contribution to the photoionization yields than the two-photon process by more than 1 order of magnitude.     

Dependence of the Er<Subscript>2</Subscript>O<Subscript>3</Subscript> selective emission on the intensity of laser thermal excitation

The dependence of the selective emission (SE) spectra of erbium oxide (Er₂O₃) in the visible and near-IR spectral ranges on the laser excitation intensity at a wavelength of 10.6 μ m is experimentally studied. The intensity ratio for the Er³⁺ electronic and vibronic transitions in the SE spectra is varied with an increase in the laser intensity to 10 kW/cm². The mechanism for the multiphonon fluctuation excitation of electronic states and a possibility for the SE application in the observation of the thermo-photo-laser effect are discussed.     

New property of the fullerenes: the anomalously effective quenching of electronically excited states owing to energy transfer to the C<Subscript>70</Subscript> and C<Subscript>60</Subscript> molecules

The quenching of the electronically excited states of various energy donors—Tb³⁺; 9,10-anthracene dibromide; and adamantanone—by C₇₀ fullerene has been detected and analyzed. The quenching is characterized by anomalously high biomolecular quenching rate constants, which are obtained from the Stern-Volmer dependences of the energy-donor photoluminescence intensity on the concentration of the C₇₀ molecules. It has been shown that the high efficiency of quenching by the C₇₀ fullerene as compared to the C₆₀ fullerene is due to the higher polarizability of the C₇₀ molecule and large overlap integrals of the energy-donor photoluminescence spectra with the absorption spectrum of the C₇₀ fullerene.     

Laser-induced nonthermal fragmentation of C60 studied by semiclassical dynamics simulation

Photofragmentation of the C₆₀ fullerene induced by ultrafast laser pulses is studied by semiclassical dynamics simulation. The simulation study is focused on the excitation below the continuum levels. A laser pulse of 40 fs (FWHM) with an effective photon energy of 2.0 eV and different intensities was selected to interact with the C₆₀ fullerene. The simulation results show that averaged fragmentation size distribution over groups of initial geometries selected at random exhibits a power law pattern with the peak at C₂ at high laser pulse intensities. The threshold for the C₆₀ fragmentation was determined. The simulation finds that as many as 55 electrons are excited from the occupied molecular orbitals to unoccupied molecular orbitals upon the laser irradiation and that the number of the fragments significantly depends on the number of electrons excited. Finally, the temperature examination seems to suggest that the nonthermal effect may play a significant role in laser fragmentation of the C₆₀ fullerene.     

Spectroscopic diagnostics of the laser erosion plasma of an AgGaS<Subscript>2</Subscript> polycrystalline target

Results are presented from experimental studies of the radiation emitted from a plasma produced in vacuum after irradiating a polycrystalline target by 1.06-μm laser radiation with an intensity of (3–5)×10⁸ W/cm². Plasma radiation from regions located at distances of 1 and 7 mm from the target is analyzed. It is shown that the main contribution to the plasma radiation in the 220–600 nm spectral range is made by transitions from the excited states of single-charged Ag⁺ and S⁺ ions. The atomic component of plasma radiation is represented by intense spectral lines corresponding to transitions from the Rydberg states of Ag and Ga atoms, whereas no resonance lines of these atoms are observed.     

On the interaction of self-assembled C<Subscript>60</Subscript>F<Subscript>18</Subscript> polar molecules with the Ni(100) surface

The current work is dedicated to investigation of the interaction between self-assembled polar molecules of fullerene fluoride C₆₀F₁₈ with the chemically active surface Ni(100) under radiation and heat treatments. X-ray photoelectron spectroscopy is used in combination with quantum-chemical simulation. For the first time, the transformation of an as-deposited dielectric continuous 2D thin film to a 3D island-type assembly with molecular ordering within the islands is shown to take place. The degree of coverage of the Ni surface by C₆₀F₁₈ islands (0.6–0.7) and their height (~6 nm) are estimated. Quantum-chemical simulation shows that the chemisorption energy of the C₆₀F₁₈ molecule on the Ni surface equals ~6.6 eV and fluorine atoms are located at a distance of 1.9 Å above the Ni surface. The results of the investigation provide an opportunity to create nanoscale ordered structures with local changes in the work function.     

Investigation of fluorination reactions of the C<Subscript>60</Subscript>Br<Subscript>24</Subscript> bromofullerene with xenon difluoride

The products of the reaction between the C₆₀Br₂₄ bromofullerene and xenon difluoride are studied by IR spectroscopy, laser desorption mass spectrometry, ¹⁹F NMR spectroscopy, and thermogravimetry. It is revealed that the degree of fluorination of the substrate is primarily determined by the duration of contact between the reactants. An attempt is made to perform nucleophilic substitution of fluorine for bromine in the C₆₀Br₂₄ bromofullerene in a solution with potassium fluoride.     

Non-adiabatic transition in C2H5OH+ on a light-dressed potential energy surface by ultrashort pump-and-probe laser pulses

We experimentally investigate how parameters of ultrashort laser pulses such as the pulse width and wavelength could induce changes in the dynamics of vibrational wave packets on the light-dressed-potential energy surface (LD-PES) of C₂H₅OH⁺ using a pump-and-probe pulse excitation scheme. The probability of non-adiabatic transition at 800 nm from the singly ionized ground state to the repulsive excited state leading to C–O bond breaking is enhanced when a probe laser pulse is delayed by ～180 fs. At this pulse delay, on the other hand, C–C bond breaking is significantly suppressed. Therefore, the deformation of LD-PES is considered to change the direction of the wave packet traveling originally along the C–C stretching into the direction along the C–O stretching. This non-adiabatic transition leading to the redirection of the dissociating wave packet is found to occur more efficiently at the probe laser wavelengths at 400 nm than at 800 nm. The critical pulse delay is still ～180 fs even at 400 nm.     

Dynamics of electron scattering between bulk states and the C<Subscript>1</Subscript> surface state of InP(100)

Hot electron dynamics was investigated, with a focus on scattering between bulk states and the C₁ surface state that is formed on the (2×4)-reconstructed In-rich surface of InP(100). The latter surface was prepared via metal organic chemical vapor deposition (MOCVD) and monitored by reflectance anisotropy spectroscopy (RAS/RDS). Two-color twophoton photoemission (2PPE) was employed with laser pulses of about 50 fs duration. Hot electrons were generated in bulk states about 0.5 eV above the C₁ surface state, thereby avoiding any significant direct optical population of the surface state. A time constant of 35 fs was determined from the experimental data for electron scattering from isoenergetic bulk states to the C₁ surface state by analyzing the rise of a C₁-specific peak in the 2PPE spectrum. The decay of this C₁ peak was ascribed to energy relaxation of the photo-generated electrons to bulk states below the surface state. Analogous measurements were carried out with a (2×1/2×2)-reconstructed P-rich surface of InP(100) that was also grown via MOCVD. No sign of a surface statewas detected in the 2PPE spectra for the latter surface in the corresponding energy range of the conduction band. PACS 73.20.-r; 78.47.+p; 79.60.-i; 79.60.Bm     

The thermionic double-diode,an efficient detector in excited state laser spectroscopy

We are describing the thermionic double-diode which is a suitable instrument for excited state laser spectroscopy. In comparison to the optogalvanic technique the signal-to-noise ratio was found to be 10²?10³ times better, investigating transitions between excited Sr or Ba states. Combined with its high detection sensitivity the thermionic double-diode presents the possibility of investigating transitions between high angular momentum states. It is demonstrated by studying transitions between Rydberg levels and doubly-excited autoionizing states in Ba. Further advantages are (i) the small strength of the dc electric field and the low electron density in the laser excitation region of the double-diode commending itself for studies of Doppler-free transitions to highly excited states and (ii) the very stable working conditions allowing to vary the pressure and current conditions in the diode in a much wider range than in a discharge.     

Spectroscopy and energy balance of the Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> selective emission upon the laser thermal excitation

The laser thermal melting of powders is used to fabricate selective emitters (SEs) that represent Nd₂O₃ and Y₂O₃-Nd₂O₃ polycrystals on quartz holders. The SEs are stable under atmospheric conditions upon multiple heating by laser radiation up to the melting point. The spectral shape and integral intensity of the selective heat radiation (SHR) of the Nd₂O₃ microcrystalline powder and the Nd₂O₃ and Y₂O₃-Nd₂O₃ polycrystals are experimentally studied in the near-IR and visible spectral ranges versus the intensity of the laser thermal excitation at a wavelength of 10.6 μm in comparison with the absorption and luminescence spectra of the YAG:Nd³⁺ and YAlO₃:Nd³⁺ single crystals. The SHR spectra are determined by the vibronic transitions between the electronic states ² G _7/2-⁴F_3/2 ⁴I_11/2 and ⁴I_9/2 of the Nd³⁺ ions that are thermally excited due to the multiphonon transitions from the ground state. The energy balance of the SE laser thermal heating is experimentally investigated. The coefficient of the laser energy conversion to the Nd³⁺ SHR is measured, and the emissivity of the SEs that can be used for the study of the thermophotovoltaic generators and the optical excitation of the laser-active media in the near-IR spectral range is estimated.     

Photopolymerization of C<Subscript>60</Subscript> and Li@C<Subscript>60</Subscript> studied by second-harmonic generation and infrared spectroscopy

The photopolymerization of C₆₀ and Li@C₆₀ films was investigated by means of optical second-harmonic generation. The films were deposited under ultra-high-vacuum conditions and irradiated in situ with an Ar⁺ laser at 514 nm. The second harmonic generated by a Nd:YAG laser working at 1064 nm was monitored after different steps of irradiation. Photopolymerization was observed after very low irradiation doses, of the order of 10²⁰ photons/cm², and confirmed with infrared absorption spectroscopy. Similar kinetics for C₆₀ and Li@C₆₀ were observed. The measurements give evidence for photopolymerization of the endohedral fullerene Li@C₆₀. PACS 78.30.Na; 82.50.Hp; 81.05.Tp