Highly localized vibronic wavepackets in large reactive molecules

The ultrafast dynamics of the internal conversion of S₁ azulene and the excited-state intramolecular proton transfer in 2-(2^′-hydroxyphenyl)benzothiazole (HBT) were investigated by pump–probe spectroscopy with tunable pulses as short as 20 fs. In both cases we find very pronounced oscillatory contributions to the transients, which are due to vibrational wavepacket motion in the excited state. The damping times are on the order of 1 ps even for these large reactive molecules in solution at room temperature. For azulene only 2 out of 48 vibrational modes participate and in HBT only 4 out of 69. This high degree of localization of the wavepacket seems to be a general feature, and supports hopes that even for systems of chemical interest coherent control might be possible. Received: 24 January 2000 / Published online: 24 July 2000     

Isotope effects in the kinetics of simultaneous H and D thermal desorption from Pd

The kinetics of simultaneous hydrogen and deuterium thermal desorption from PdH_xD_y has been investigated. A novel experimental approach for the study of the transition state (TS) characteristics of the surface recombination reaction is proposed based on the analysis of the H and D partitioning into H₂, HD and D₂ molecules. It has been found that the hydrogen molecular isotopes distribution is determined by the energy differences of the corresponding TS of the atom-atom recombination reactions. On the other hand, the mechanisms and activation energies of the desorption process have been obtained. At 420 K, the desorption reaction changes from a surface recombination limiting mechanism during desorption from β-PdH_xD_y to a reaction limited by the rate of β to α phase transformation during the two phase coexistence. Surface recombination reaction becomes again rate limiting above 480 K, due to a change in the catalytic properties of the Pd surface. TS energies obtained from the kinetic analysis of the thermal desorption spectra are in good accordance with those obtained from the analysis of the H₂, HD and D₂ distributions. Anomalous TS energies have been observed for the H-D recombination reaction, which may be related to the heteronuclear character of this molecule.     

A polarized CARS investigation of the fine structure population inversion of Cl atoms from laser photolysis of ICl and the quenching of Cl(2 P 1/2) by O2

The time resolved polarized CARS technique has been used to detect Cl atoms produced by photolysis of ICl in the presence and absence of O₂. A population inversion was observed between the ground state electronic levels Cl(² P _1/2) and Cl(² P _3/2). The rate constant for Cl(² P _1/2) decay (quenching + reaction) in ICl was determined to be (3.2±0.2)×10^–13 cm³/molecule×s; the rate constant for Cl(² P _3/2) reaction with ICl was determined to be (7.8±0.5)×10^–12 cm³/molecule×s; and the rate constant for Cl(² P _1/2) quenching by O₂ was determined to be (1.9±0.2)×10^–13 cm³/molecule×s.     

Photostimulated chemistry at the metal-adsorbate interface

The ultraviolet photochemistry of molecules adsorbed on metallic surfaces has been studied using excimer lasers as radiation source. Dissociation with the fragments either ejected into the gas phase or retained on the surface is one prominent channel. The other is photodesorption of intact molecules. The desorbing molecules are characterized by time-of-flight mass spectroscopy and laser spectroscopy. The state of the adsorbate after irradiation is characterized by thermal desorption spectroscopy and high resolution electron energy loss spectroscopy. The methods and fundamental characteristics are exemplified using results from three studied systems: O₂, H₂O, and N₂O₄ adsorbed on Pd(111).     

Non-linear scission/recombination kinetics of living polymerization

Living polymers are formed by reversible association of primary units (unimers). Generally the chain statistical weight involves a factor σ < 1 suppressing short chains in comparison with free unimers. Living polymerization is a sharp thermodynamic transition for σ ≪ 1 which is typically the case. We show that this sharpness has an important effect on the kinetics of living polymerization (one-dimensional association). The kinetic model involves i) the unimer activation step (a transition to an assembly-competent state); ii) the scission/recombination processes providing growth of polymer chains and relaxation of their length distribution. Analyzing the polymerization with no chains but unimers at t = 0 , with initial concentration of unimers M ≳ M ^* (M^* is the critical polymerization concentration), we determine the time evolution of the chain length distribution and find that: 1) for M ^* ≪ M ≪ M ^*/σ the kinetics is characterized by 5 distinct time stages demarcated by 4 characteristic times t₁, t₂, t₃ and t^*; 2) there are transient regimes (t ₁ ≲ t ≲ t ₃) when the molecular-weight distribution is strongly non-exponential; 3) the chain scissions are negligible at times shorter than t₂. The chain growth is auto-accelerated for t ₁ ≲ t ≲ t ₂ : the cut-off chain length (= polymerization degree 〈n〉_w N ₁ ∝ t ² in this regime. 4) For t ₂ < t < t ₃ the length distribution is characterized by essentially 2 non-linear modes; the shorter cut-off length N₁ is decreasing with time in this regime, while the length scale N₂ of the second mode is increasing. (5) The terminal relaxation time of the polymer length distribution, t^*, shows a sharp maximum in the vicinity of M^*; the effective exponent is as high as ∼ σ^-1/3 just above M^*.     

Role of vitreous matrix on the optical activity of Ge-doped silica

We report an experimental study on the relationship between the optical activity of Ge-oxygen deficient centers and dynamic properties and conformational heterogeneity of vitreous matrix in silica. We focus our attention on the absorption band at ∼5.2 eV (B_2β) and on the two related emissions at ∼4.2 eV (α_E) and at ∼3.1 eV (β). From the temperature dependence of B_2β band we estimate a mean energy value of 26 meV for local vibrational modes coupled to the electronic transition, suggesting that the chromophore and its surrounding have access to low frequency dynamics. From the thermal behavior of the two emissions we distinguish the two competitive relaxation processes from the first singlet excited state S₁: the radiative one, giving rise the α_E band, and the thermally activated intersystem-crossing process between S₁ and the triplet state T₁, originating the β band. The intersystem-crossing rate increases on increasing the temperature, determining an opposite thermal behavior of the intensity of the two emissions. However, this temperature dependence cannot be rationalized by a simple Arrhenius law and the α_E decay kinetics at high temperatures do not follow a single exponential law, suggesting a complex landscape of configurational energies of the process.     

Density functional theory investigation of S2 in KCl: evidence for the existence of a di-vacancy site

Electron paramagnetic resonance experiments have shown that, depending on the doping procedure, two different S₂⁻ centers may coexist in KCl. These centers have the ²B_2g and the ²B_3g ground state, respectively. As no experimental ligand hyperfine data are available, it could not be determined whether the S₂⁻ molecular ion replaces a single halide ion (mono-vacancy site) or two nearest neighbor halide ions (di-vacancy site). Also, other defect models could a priory be considered. In this work, cluster in vacuo density functional theory calculations of the g and ³³S hyperfine tensors show that the S₂⁻ ion at a mono-vacancy site has the ²B_2g ground state, whereas S₂⁻ in a di-vacancy exhibits a ²B_3g ground state. For the latter center, the possibility of charge compensation by a cation vacancy is also considered. The calculations indicate that a possible vacancy is not in the direct vicinity (nearest or next-nearest neighbor) of the S₂⁻ ion.     

Van Vleck paramagnetism of the trivalent Eu ions

Magnetic susceptibilities of Eu₂O₃, EuF₃ and EuBO₃ have been measured over the wide temperature range 5-650 K. The Van Vleck paramagnetism, with the ground state of ⁷F₀ (S=3, L=3), has been investigated comprehensively. The temperature independent paramagnetism emerges manifestly below approximately 100 K. The variation of the susceptibility with temperature for EuBO₃ is in satisfactory agreement with the coupling constant , where the spin-orbit interaction is λL·S for the Russell-Saunders coupling on the basis of Van Vleck theory with one parameter λ. The value of can fit the susceptibility data of EuF₃. The deviation from the theory arises in Eu₂O₃. This discrepancy originates mainly from the influence of the crystalline field. Susceptibility of Gd₂O₃, having the ground state of ⁸S_7/2 (S=7/2, L=0), is also presented as a magnetic standard compound in comparison with these results.     

NDMAP: the best material to study the Haldane's prediction

As predicted by Haldane, spin, S=1 one-dimensional (1D) Heisenberg antiferromagnet (HAF) has an energy gap between the singlet ground state and first excited triplet. On application of magnetic field, the triplet state Zeeman splits and the energy of one of the triplet state becomes zero at a critical field, H_c. Above H_c the system recovers magnetism. Then, we expect that a quasi-1D HAF will show a magnetic long-range ordering (LRO) at low temperatures due to the inter-chain coupling. This field-induced LRO has not been observed before due to complication of the crystal structure in the materials studied so far and/or technical difficulty.From a heat capacity measurement on a single crystal of an S=1 quasi-Q1D HAF, Ni(C₅H₁₄N₂)₂N₃(PF₆), we found an anomaly at a temperature in finite fields indicating a field-induced phase transition. A magnetic LRO is confirmed by a neutron diffraction measurement on the same sample. The temperature versus magnetic field phase diagram of this compound is constructed and discussed.     

Angle and speed distributions of hydrogen desorbing thermally from metal surfaces

A quantum theoretical treatment of the angle and speed distributions of recombinatively desorbing hydrogen from metal surfaces is proposed. The desorption rate is discussed in the framework of the transition state theory. The recombinative reaction process of hydrogen due to thermal activation leads to the formation of an activated complex in the transition state. In the vicinity of a saddle point on a three-dimensional potential energy surface, the translational motion of the activated complex in the direction perpendicular to the metal surface is accompanied by its center-of-mass vibrational motion parallel to the metal surface. In order to carry out the quantum mechanical calculation, the potential surface is replaced by a simplified model potential, which provides a square potential barrier along the surface normal. It is shown that, on leaving the potential barrier, the activated complex is reflected by the boundary of the potential barrier with a certain probability and, at the same time, the center-of-mass modes of vibration with frequencies v ₁ and v ₂ are coupled with the translational motion along the surface normal. Vibrational wave functions in the momentum representation are used to calculate the transmission coefficient, which is incorporated into the conventional rate formula. The angle-dependent speed distributions of desorbing molecules are derived from the rate formula.     

Higher order two step mechanisms in nucleon antinucleon annihilation and the OZI rule

We evaluate three meson doorway mechanisms for nucleon-antinucleon annihilation at rest for the first time. Detailed results are presented for the final state φπ⁰ originating from the ³S₁ initial state and for the φρ channel originating from ¹S₀. The results presented also include the improved contributions from two meson doorway states and from the tree diagrams. For all the channels considered a consistent explanation of large and small OZI violations emerges. Received: 22 December 1999     

Perturbative approach to anA+B→C reaction-diffusion system

The hierarchy of kinetic equations for diffusion-reaction processes are rederived using a Fock space formalism for the Master equation. In the diffusion dominated case the reactive part can be analyzed perturbationally. In according to the experimental situation the behaviour of the system is governed by one space dimension. The summation of a whole class of terms in a perturbative serie yields the scaling behaviour of the production rate of the C particle. The solution depends on the ratio of the diffusion constantsD=D _A /D _B and the ratio of the characteristic time scales for reaction and diffusion, respectively. Various special cases and approximations are discussed in terms ofD. The analytical results can be supported by numerical simulations.     

Measurements of photoionization cross sections from the 4p, 5d and 7s excited states of potassium

New measurements of the photoionization cross sections from the 4p ²P_1/2,3/2, 5d ²D_5/2,3/2 and 7s ²S_1/2 excited states of potassium are presented. The cross sections have been measured by two-step excitation and ionization using a Nd:YAG laser in conjunction with a thermionic diode ion detector. By applying the saturation technique, the absolute values of the cross sections from the 4p ²P_3/2 and 4p ²P_1/2 states at 355 nm are determined as 7.2±1.1 and 5.6±0.8 Mb, respectively. The photoionization cross section from the 5d ²D_5/2,3/2 excited state has been measured using two excitation paths, two-step excitation and two-photon excitation from the ground state. The measured values of the cross sections from the 5d ²D_5/2 state by two-photon excitation from the ground state is 28.9±4.3 Mb, whereas in the two-step excitation, the cross section from the 5d ²D_3/2 state via the 4p ²P_1/2 state and from the 5d ²D_5/2,3/2 states via the 4p ²P_3/2 state are determined as 25.1±3.8 and 30.2±4.5 Mb, respectively. Besides, we have measured the photoionization cross sections from the 7s ²S_1/2 excited state using the two-photon excitation from the ground state as 0.61±0.09 Mb.     

Luminescence characteristics of ultraviolet upconversion from Er 3 + :YAG crystal by Ar + laser (488 nm) excitation

Ultraviolet and violet upconversion signals at 271 nm, 317 nm, 381 nm and 407 nm were observed when an erbium-doped YAG crystal was pumped by an Ar⁺ laser (488 nm). The dependence of intensity of luminescence emitting from the ⁴S _3/2 state and the ²P _3/2 state on pump power (I) was experimentally investigated. Changes from I¹ down to I ^1/2 for the ⁴S _3/2 state and from I² down to I¹ for the ²P _3/2 state were observed. The upconversion mechanism was discussed by means of the rate equations. It appears that energy-transfer upconversion (ETU) is a dominant process for the Er³⁺:YAG crystal used in our experiment. Received 20 March 2001 and Received in final form 11 July 2001     

Optimizing the production of metastable calcium atoms in a magneto-optical trap

We investigate the production of long-lived metastable (4³ P ₂ ) calcium atoms in a magneto-optical trap (MOT) operating on the 4¹ S ₀ ?4¹ P ₁ transition at 423 nm. For excited 4¹ P ₁ atoms a weak decay channel into the triplet states 4³ P ₂ and 4³ P ₁ exists via the 3¹ D ₂ state. The undesired 4³ P ₁ atoms decay back to the ground state within 0.4 ms and can be fully recaptured if the illuminated trap volume is sufficientlylarge. We obtain a flux of above 10¹⁰ atoms/s into the 4³ P ₂ state. We find that our MOT lifetime of 23 ms is mainly limited by this loss channel, and thus the 4³ P ₂ production is not hampered by inelastic collisions. If we close the loss channel by repumping the 3¹ D ₂ atoms with a 671 nm laser back into the MOT cycling transition, a non-exponential 72 ms trap decay is observed, indicating the presence of inelastic two-body collisions between 4¹ S ₀ and 4¹ P ₁ atoms. Received: 10 July 2001 / Revised version: 22 October 2001 / Published online: 23 November 2001     

The beryllium atom and beryllium positive ion in strong magnetic fields

The ground and a few excited states of the beryllium atom in external uniform magnetic fields are calculated by means of our 2D mesh Hartree-Fock method for field strengths ranging from zero up to 2.35×10⁹ T. With changing field strength the ground state of the Be atom undergoes three transitions involving four different electronic configurations which belong to three groups with different spin projections S _z = 0, - 1, - 2. For weak fields the ground state configuration arises from the 1s ²2s ², S _z = 0 configuration. With increasing field strength the ground state evolves into the two S _z = - 1 configurations 1s ²2s2p _-1 and 1s ²2p _-13d _-2, followed by the fully spin polarised S _z = - 2 configuration 1s2p _-13d _-24f _-3. The latter configuration forms the ground state of the beryllium atom in the high field regime γ > 4.567. The analogous calculations for the Be ⁺ ion provide the sequence of the three following ground state configurations: 1s^22s and 1s ²2p _-1 (S _z = - 1/2) and 1s2p _-13d _-2 (S _z = - 3/2). Received 2 October 2000 and Received in final form 8 January 2001     

The Contribution of Raman Scattering to the Fluorescence of the Polyene Antibiotic Amphotericin B

Fluorescence has recently been applied to the analysis of the molecular organization state of the polyene antibiotic amphotericin B (AmB) in solution or in lipid membranes. The polyene chain of AmB monomer gives rise to two fluorescence emissions; S₁(2¹A_g) → S₀(1¹A_g) between 500 and 700 nm, S₂(1¹B_u) → S₀(1¹A_g) between 400 and 500 nm. However, Raman scattering might interfere with the S₂ → S₀ emission fluorescence due to the weak fluorescence quantum yield and close proximity to the exciting lines. In fact, we show here that a change in the excitation wavelength results in a shift of three emission bands, an effect which excludes their assignment to fluorescence. These bands originate from the water Raman at 3382 cm^-1and AmB resonance Raman at 1556 and 1153 cm^-1. As a consequence, some former conclusions on the molecular organization state of AmB should be reconsidered.     

Photo-excitation from dia- to ferri-magnetism in a Rb-Co-hexacyanoferrate Prussian blue analogue

We studied the photo-excitation process, the relaxation of the photo-excited state towards the stable state, and the photo-induced magnetic properties of the Prussian blue analogue Rb_0.52Co [Fe(CN)₆]_0.84, 2.3 H₂O. Magnetic, M?ssbauer and reflectivity measurements have been performed during and after illumination. The efficiency of the photo-excitation device is maximum at nm. The process, however, is severely hindered by bulk absorption of the light; it is rapidly completed at the surface of the sample and then proceeds slowly in the bulk. Under the effect of photo-excitation the system turns from a dia- to a ferri- magnet, with a value K, indicative of the transformation of the material due to the following optical electron transfer: Thermal relaxation towards the stable electronic state is observed in the 95-110 K temperature interval, obeying a self-accelerated kinetics. At low temperature, a weak, non-exponential, relaxation is detected. These features are discussed in terms of co-operative effects in the frontal process of photo- excitation. The peculiarities of a photo-excited state created below the magnetic ordering temperature are discussed. A metastable magnetic state has been observed in low fields, denoted “Raw Photo-Induced State" (RPI), with a magnetization curve in-between the field-cooled and zero-field-cooled curves. Received 12 March 1999 and Received in final form 11 December 1999     

First-principles study on the electronic structure and magnetic properties of metallic antiferromagnet C7H3S2N2

First-principles full potential linearized augmented plane wave (FPLAPW) calculations have been performed to study the electronic structure and the magnetic properties of 3-Cyanobenzo-1,3,2-dithiazolyl,C₇H₃S₂N₂. The density of states (DOS), the total energy of the cell, and the spontaneous magnetic moment of C₇H₃S₂N₂ were all calculated. The calculations reveal that the low-temperature phase of the compound C₇H₃S₂N₂ has a stable metal-antiferromagnetic ground state, and there exists an antiferromagnetically coupled interactions between the dithiazolyl radical(1), which is in good agreement with experiment.     

Angle and speed distributions of hydrogen desorbing thermally from metal surfaces

On the basis of the theory developed in a previous paper (Part I), the angle and speed distributions of D₂ molecules desorbing thermally from the Ni(111) surface are numerically calculated in the present paper (Part II). The dynamical motion of the activated complex of the recombinative desorption process is calculated by using a model potential surface, which involves a few parameters introduced to describe the necessary features of the potential surface at the transition state. Numerical calculations are carried out, and the results show that the present dynamical theory reproduces very well a variety of the characteristic features of the experimental results, e.g., sharply focused angular distribution, mean translational energy lower than 2k _B T at grazing angle, and the non-Maxwellian profile of the TOF distribution.