Modelization of the fragmentation dynamics of krypton clusters (Kr(n),n=2-11) following electron impact ionization

We present the first prediction for the fragmentation dynamics following electron impact ionization of neutral krypton clusters from 2 to 11 atoms. Fragment proportions and parent ion lifetimes are deduced from a molecular dynamics with quantum transitions study in which the nuclei are treated classically and the transitions between electronic states quantum mechanically. The potential-energy surfaces are derived from a diatomics-in-molecules model to which induced dipole-induced dipole and spin-orbit interactions are added. The results show surprisingly fast and extensive fragmentation for clusters of such a heavy atom, although not as extensive as in the case of neon clusters studied previously [D. Bonhommeau et al., J. Chem. Phys. 123, 54316 (2005)]. The parent ion lifetimes range from 2.8 to 0.7 ps, and the most abundant fragment is Kr(2) (+) for all studied sizes, followed by Kr(+) for sizes smaller than 7 atoms and by Kr(3) (+) for larger sizes. Trimer and larger fragments are found to originate from the lower electronic states of parent ions. The comparison with preliminary results from experiments on size-selected neutral clusters conducted by Steinbach et al. (private communication) reveal a good agreement on the extensive character of the fragmentation. It is checked that the additional internal energy brought by the helium scattering technique used for size selection does not affect the fragment proportions. In addition, the existence of long-lived trajectories is revealed, and they are found to be more and more important for larger cluster sizes and to favor the stabilization of larger fragments. The implications of this work for microsecond-scale dynamics of ionized rare-gas clusters are discussed. In particular, given the extent of fragmentation of the parent clusters and the fast kinetics of the whole process, the small cluster ions that exhibit a monomer loss in the microsecond time window must originate from much larger neutral precursors. The decay rate of the II(12)(u) state of the ionic dimer Kr(2) (+) by spin-orbit coupling is found to be of the order of 3 ps, in contrast to the expected tens of microseconds, but only reasonably faster than the corresponding state of HeNe(+). Finally, the spin-orbit interaction strongly affects both the Kr(+)Kr(2) (+) ratio and some of the characteristic times of the dynamics, especially for smaller sizes, but not the overall dependence of the fragment proportions as a function of cluster size.     

Ultrafast fragmentation and ionisation dynamics of ammonia clusters

The formation of protonated and unprotonated ammonia cluster ions is studied by femtosecond two colour two photon pump-probe techniques applied to (NH₃) _n and (ND₃) _n clusters withn up to 8. The fourth harmonic (～ 200 nm, 6.2 eV, 160 fs) of a Ti: Sapphire laser pulse is used to excite the clusters in a state corresponding to theà state of NH₃ while the third harmonic (267 nm, 4.65 eV) is used for the subsequent ionisation step. Employing a combination of the optical Bloch equations for the excitation process and rate equations for the cluster dynamics we calibrate the zero time delay and carefully analyse the time dependence of the pump-probe signal. Several distinct intermediate steps in the time evolution can be distinguished, having characteristic time constants ranging from 40 fs to over 100 ps. They are discussed in a consistent scheme for the excitation, ionisation and protonation dynamics, accounting also for characteristic differences observed between deuterated and undeuterated species. A particularly remarkable time dependence of the homogeneous (NH₃) ₂ ⁺ cluster ion signal is interpreted as a fingerprint of internally protonated neutral precursors of the type NH₃NH₂NH₄.     

Energy flow in push-pull chromophores: vibrational dynamics in para-nitroaniline.

para-Nitroaniline (PNA) plays an essential role as the prototype model of push-pull chromophores. The nature and degree of participation of vibrational degrees of freedom in the charge-transfer and internal-conversion processes are current issues of great theoretical and practical importance. Ultrafast time-resolved anti-Stokes resonance Raman spectroscopy (TRARRS) experiments on PNA in dimethyl sulfoxide with three different excitation wavelengths were performed to probe these dynamical influences. The vibrational dynamics associated with S0 were independent of incident wavelength, and this supports the picture that the S1 dynamics are fast relative to the rate of intersystem crossing. The phenyl breathing mode nu(19) (860 cm(-1)) and the symmetric NO2 stretch nu(29) (1310 cm(-1)) exhibited vibrational lifetimes in S0 of 8.1 and 5.2 ps, respectively. No evidence for inhomogeneous broadening of the charge-transfer band in the UV/Vis absorption spectrum was found.     

Theoretical study of the fragmentation and reactivity of Sn molecules,where n≤8

V. Kapsukas Vil'nyus State University. Scientific-Research Institute of Chemicals for Polymer Materials, Tambov. Translated from Zhurnal Strukturnoi Khimii, Vol. 29, No. 2, pp. 19–23, March–April, 1988.     

The structure and fragmentation of B n (n≥3) ions in peptide spectra

The unimolecular and low energy collision-induced fragmentation reactions of the MH⁺ ions of N-acetyl-tri-alanine, N-acetyl-tri-alanine methyl ester, N-acetyl-tetra-alanine, tetra-alanine, penta-alanine, hexa-glycine, and Leu-enkephalin have been studied with a particular emphasis on the formation and fragmentation of B _n (n=3,4,5) ions. In addition, the metastable ion fragmentation reactions of protonated tetra-glycine, penta-glycine, and Leu-enkephalin amide have been studied. B _n ions are prominent stable species in all spectra. The B _n ions fragment, in part, by elimination of CO to form A _n ions; this reaction occurs on the metastable ion time scale with a substantial release of kinetic energy (T _1/2=0. 3–0. 5 eV) that indicates that a stable configuration of the B _n ion fragments by way of a reacting configuration that is higher in energy than the fragmentation products, A _n + CO. Ab initio calculations strongly suggest that the stable configuration of the B₃ and B₄ ions is a protonated oxazolone formed by interaction of the developing charge with the next-nearest carbonyl group as HX is lost from the protonated species H-(Yyy) _n -X · H⁺. The higher B _n ions also fragment, in part, to form the next-lower B ion, presumably in its stable protonated oxazolone form. This reaction is rationalized in terms of the three-dimensional structure of the B _n ions and it is proposed that the neutral eliminated is an α-lactam.     

Energy dependence of the fragmentation of ester enolate ions

The energy dependence of the fragmentation of a selection of ester enolate ions has been studied by variable, low-energy collision-induced dissociation experiments in the quadrupole collision cell of a hybrid BEQQ mass spectrometer. The dominant fragmentation reactions observed are where ΔH₁ ? ΔH₂=PA([RCCO]^?) ? PA([?O]^?) (PA=proton affinity). The anion of lowest proton affinity is formed preferentially at low internal energies with the yield of the anion of higher proton affinity increasing with increasing internal energy. The [CH₃OCOCOCH₂]^? anion derived from methyl pyruvate forms [CH₃OCO]^? by reaction (2); this anion readily fragments to [CH₃G]^?+ CO consistent with a structure represented by a dipole-stabilized cluster of [CH₃O]^? and CO. Comparison of the 8-keV with the 50-eV collision-induced dissociation mass spectra indicated that the average internal energy of the fragmenting ions is considerably lower in the high-energy collisional experiments than it is in the low-energy collisional experiments.     

Molecular dynamics simulations of extensional,sheet and unidirectional flow

Non-equilibrium molecular dynamics, NEMD, has been used to determine the technologically important tensile viscosities. Simulations of elongational, sheet and unidirectional viscoelastic responses via the “differences-in-trajectories” technique have been made on Lennard-Jones liquid at ?* = 0.8442 and T* = 0.72, and ?* = 1.01304 and T* = 1.26. At finite strain rates (·γ* ≥ 0.1) shear thinning behavior is evident, in particular for unidirectional (“poker chip”) extensional flow. At γ ≥ 0.4 steady state unidirectional viscosities were not achieved before severe material deterioration. These trends are the result of extremely complex structural reorganisation well within the viscoelastic regime, which involved coupled component relaxation moduli along distortion direction.     

Dissociative double electron capture,dynamics of fragmentation of the water and hydrogen sulfide negative ions

The technique of ion kinetic energy spectrometry has been used to observe the unimolecular decompositions of H₂O^?? and H₂S^?? generated by charge exchange of the corresponding high velocity positive ions. The method involves dissociative double electron capture by a high velocity ion and allows the study of unstable negative ions that may be directly observable by conventional electron capture techniques. Information on the energetics of the reaction is obtained from the kinetic energy of the product ion. The reactions under consideration are shown in (1) and (2) where X = O or S.

The kinetic energy releases accompanying the reactions given in (1) and (2) have been measured and compared to those for the collision-induced reactions which produce the corresponding positive ions. The results have been used to deduce that the sequence of steps in the formation of the fragment negative ions is that given in (1) and (2). The cross section of OH^? formation is observed to be somewhat greater than for O^? production. This result is in contrast with dissociative electron capture cross sections from the neutral species and is interpreted on the basis of the energetic requirements for the reactions under consideration. H₂O^? reacts from different electronic states in yielding OH^? on the one hand and O^? on the other. The energy partitioning associated with reaction (2) suggests that the neutral productions 2H' rather than H₂. The kinetic energy losses accompanying excitation and kinetic energy releases upon fragmentation were similar for the corresponding reactions of the sulfur and oxygen-containing ions indicating related mechanisms in the two sets of reactions.     

Radiative relaxation and fragmentation dynamics of S 2p-excited hydrogen sulfide

Radiative relaxation of S 2p-excited hydrogen sulfide (H(2)S) is investigated by dispersed ultraviolet and visible fluorescence spectroscopies. We observe distinct changes in the fluorescence spectra as a function of excitation energy. Excitation to Rydberg states below the S 2p ionization threshold yields intense fluorescence from neutral and ionic atomic fragments (H, S(+), and S(2+)). In addition to the atomic emission, fluorescence of the molecular fragment ion HS(+) is preferably found after excitation of the S 2p electron into the unoccupied 6a(1) and 3b(2) orbitals with sigma(*) character. This is interpreted as evidence for ultrafast dissociation of the core-excited molecule prior to electronic relaxation. The rotationally resolved fluorescence spectra of the A (3)Pi-->X (3)Sigma(-) transition are analyzed in terms of the fragmentation dynamics leading to the formation of the excited molecular fragment ion, where changes in bond angle are discussed in terms of the rotational population.     

Effect of the basic residue on the energetics, dynamics, and mechanisms of gas-phase fragmentation of protonated peptides

The effect of the basic residue on the energetics, dynamics, and mechanisms of backbone fragmentation of protonated peptides was investigated. Time-resolved and collision energy-resolved surface-induced dissociation (SID) of singly protonated peptides with the N-terminal arginine residue and their analogues, in which arginine is replaced with less basic lysine and histidine residues, was examined using a specially configured Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS). SID experiments demonstrated different kinetics of formation of several primary product ions of peptides with and without arginine residue. The energetics and dynamics of these pathways were determined from Rice-Ramsperger-Kassel-Marcus (RRKM) modeling of the experimental data. Comparison between the kinetics and energetics of fragmentation of arginine-containing peptides and the corresponding methyl ester derivatives provides important information on the effect of dissociation pathways involving salt bridge (SB) intermediates on the observed fragmentation behavior. Because pathways involving SB intermediates are characterized by low threshold energies, they efficiently compete with classical oxazolone and imine/enol pathways of arginine-containing peptides on a long time scale of the FTICR instrument. In contrast, fragmentation of histidine- and lysine-containing peptides is largely determined by canonical pathways. Because SB pathways are characterized by negative activation entropies, fragmentation of arginine-containing peptides is kinetically hindered and observed at higher collision energies as compared to their lysine- and histidine-containing analogues.     

Ab initio lattice dynamics of nonconducting crystals by systematic fragmentation

A systematic method for approximating the ab initio electronic energy of crystal lattices has been improved by the incorporation of long range electrostatic and dispersion interactions. The effect of these long range interactions on the optimization of the crystal structure is reported. The harmonic lattice dynamics have been evaluated to give phonon frequencies and neutron scattering intensities. Exemplary results are reported for diamond, silicon, and α-quartz using Hartree-Fock, M?ller-Plesset perturbation, and coupled-cluster levels of ab initio theory.     

Collision induced fragmentation of mass-selected (CO2) n + clusters

The collisional velocity dependence of the cross sections for fragmentation of mass-selected (CO₂) _n ⁺ (n+2...7) clusters in collisions with Ar atoms is presented. Interesting structure can be observed in the cross sections which indicate that the collision occurs between the Ar atom and one CO₂ molecule within the cluster. The results may be explained by assuming that the collision leads to either vibrational excitation of a loosely bound CO₂ monomer which then leaves the cluster or excitation of the entire cluster to a dissociative state.     

Energetics and dynamics of peptide fragmentation from multiple-collision activation and surface-induced dissociation studies

This account summarizes the energetics and dynamics of peptide fragmentation obtained using a new approach recently developed in our laboratory. The approach involves RRKM modeling of time- and energy- resolved tandem mass spectrometry (MS/MS) data obtained using collisional activation. We demonstrate that surface-induced dissociation (SID) on a long time-scale of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is perfectly suited for studying the energetics and dynamics of peptide fragmentation. The advantages provided by SID include very fast ion activation, which eliminates possible discrimination against higher-energy dissociation pathways, and efficient "amplification" of small changes in dissociation parameters. We present a summary of results obtained for small alanine-containing peptides as well as larger peptides including angiotensin analogs and a series of peptides containing the LDIFSDF motif.     

Thermodynamics,viscous flow and relaxation dynamics of bulk glass-forming Pd alloys

Experimental results concerning the thermodynamic excess properties and the equilibrium shear viscosity of the undercooled liquid state are presented, which were consistently obtained on Pd-rich bulk metallic glasses of different stability by applying the concept of the limiting fictive temperature. These results are evaluated with respect to the stability criteria that are controlling vitrification. In addition, modulated-temperature calorimetry has been performed to obtain the average relaxation time of the cooperative liquid modes near the glass transition directly in dependence of temperature. The results are compared to data obtained from static non-equilibrium measurements and discussed with respect to the relation between fragility and thermal stability of Pd-rich bulk glass-forming alloys.     

Structural dynamics and energy flow in Rydberg-excited clusters of N,N-dimethylisopropylamine

In molecular beams, the tertiary amine N,N-dimethylisopropyl amine can form molecular clusters that are evident in photoelectron and mass spectra obtained upon resonant multiphoton ionization via the 3p and 3s Rydberg states. By delaying the ionization pulse from the excitation pulse we follow, in time, the ultrafast energy relaxation dynamics of the 3p to 3s internal conversion and the ensuing cluster evaporation, proton transfer, and structural dynamics. While evaporation of the cluster occurs in the 3s Rydberg state, proton transfer dominates on the ion surface. The mass-spectrum shows protonated species that arise from a proton transfer from the alpha-carbon of the neutral parent molecule to the N-atom of its ionized partner in the dimer. DFT calculations support the proton transfer mechanism between tightly bonded cluster components. The photoelectron spectrum shows broad peaks, ascribed to molecular clusters, which have an instantaneous shift of about 0.5 eV toward lower binding energies. That shift is attributed to the charge redistribution associated with the induced dipoles in surrounding cluster molecules. A time-dependent shift that decreases the Rydberg electron binding energy by a further 0.4 eV arises from the structural reorganization of the cluster solvent molecules as they react to the sudden creation of a charge.     

Energy transfer dynamics of nanocrystal-polymer composites

Steady-state and time-resolved photoluminescence spectroscopy are used to examine the photoluminescent properties of nanocrystal-polymer composites consisting of colloidal PbS nanocrystals blended with poly(2-methoxy-5(2-ethylhexyloxy)-p-phenylene vinylene). Quenching of the emission from the conjugated polymer due to the PbS nanocrystals is observed along with band edge emission from the ligand capped PbS nanocrystals. A decrease in the photoluminescence lifetime of MEH-PPV is also observed in the thin film nanocrystal-polymer composite materials. Photoluminescence excitation spectroscopy of the PbS nanocrystal emission from the composite shows features attributed to MEH-PPV providing evidence of a F?rster transfer process.     

Excited state dynamics and fragmentation channels of the protonated dipeptide H2N-Leu-Trp-COOH

The excited state dynamics of the isolated and protonated peptide H(2)N-Leu-Trp-COOH are analyzed by fs pump-probe spectroscopy. The peptides are brought into the gas phase by electrospray ionization, and fs pump-probe excitation is detected by fragment ion formation. The pump laser addressed the excited pipi* state of the indole chromophore of the amino acid tryptophan. The subsequent excited state dynamics agreed with a biexponential decay with time constants of 500 fs and 10 ps. This is considerably shorter than the lifetime of neutral tryptophan in solution and in proteins, but similar to isolated, protonated tryptophan. Several models are discussed to explain the experimental results but the detailed quenching mechanism remains unresolved.     

Energy landscapes: topographies, interparticle forces and dynamics, and how they are related

Many-body systems exhibit dynamic behavior ranging between two extremes that can be characterized as structure-seeking and glass-forming, when allowed to cool to a solid structure from a melt or high-energy random structure. This discussion reviews what has been learned about the origins of these two kinds of behavior, in terms of how long-range forces give rise to relatively smooth energy landscapes, cooperative behavior and structure-seeking character, while short-range interparticle forces do the opposite and induce glass-forming character.     

Gas-phase properties and fragmentation behavior of cationic, dinuclear iron chloride clusters Fe(2)Cl(n)()(+) (n = 1-6)

Sector-field mass spectrometry is used to probe the fragmentation patterns of cationic dinuclear iron chloride clusters Fe(2)Cl(n)()(+) (n = 1-6). For the chlorine-rich, high-valent Fe(2)Cl(n)()(+) ions (n = 4-6), losses of atomic and molecular chlorine prevail in the unimolecular and collision-induced dissociation patterns. Instead, the chlorine deficient, formally low-valent Fe(2)Cl(n)()(+) clusters (n = 1-3) preferentially undergo unimolecular degradation to mononuclear FeCl(m)()(+) ions. In addition, photoionization is used to determine IE(Fe(2)Cl(6)) = 10.85 +/- 0.05 eV along with appearance energy measurements for the production of Fe(2)Cl(5)(+) and Fe(2)Cl(4)(+) cations from iron(III) chloride vapor. The combination of the experimental results allows an evaluation of some of the thermochemical properties of the dinuclear Fe(2)Cl(n)()(+) cations: e.g., Delta(f)H(Fe(2)Cl(+)) = 232 +/- 15 kcal/mol, Delta(f)H(Fe(2)Cl(2)(+)) = 167 +/- 4 kcal/mol, Delta(f)H(Fe(2)Cl(3)(+)) = 139 +/- 4 kcal/mol, Delta(f)H(Fe(2)Cl(4)(+)) = 113 +/- 4 kcal/mol, Delta(f)H(Fe(2)Cl(5)(+)) = 79 +/- 5 kcal/mol, and Delta(f)H(Fe(2)Cl(6)(+)) = 93 +/- 2 kcal/mol. The analysis of the data suggests that structural effects are more important than the formal valency of iron as far as the Fe-Cl bond strengths in the Fe(2)Cl(n)()(+) ions are concerned.