Formation and photofragmentation properties of isolated aromatic amino acid-silver cluster hybrids

The formation of isolated [ (Trp-2H)+Ag₉] ⁺ and [ (Tyr-2H)+Ag₉] ⁺ amino-acid-Ag₉ hybrids is reported. The photofragmentation yields of the aromatic amino acid-silver cluster hybrids, as well as those of the protonated tryptophan and tyrosine molecules ([Trp+H]⁺ and [Tyr+H]⁺) have been recorded. The fragmentation yields of the complexes are higher than the yields for [Trp+H]⁺and [Tyr+H]⁺ and present an extension of the fragmentation on the red side of the spectrum. The photofragmentation spectrum of [ Trp+Ag₉] ⁺ was recently reported [Mitric et al., J. Chem. Phys. 127, 134301 (2007)]. While the optical spectra of substituted [ (Trp-2H)+Ag₉] ⁺ and non-substituted [ Trp+Ag₉] ⁺ complexes are very similar, a strong modification of the fragmentation channels between the two complexes is observed. The fragmentation channels are sensitive to the type of bonding in aromatic amino acid-silver cluster hybrids and can be used as fingerprints of structures.     

Fragmentation Study of Globularin Through Positive and Negative ESI/MS,CID/MS,and Tandem MS/MS

Abstract

The structure of globularin was studied by a mass spectrometric methodology based on the combined use of positive and negative electrospray ionization, collision‐induced dissociation (CID), and tandem mass spectrometry. The mass spectrometry investigation was achieved through in‐source fragmentation of the deprotonated [M?H]^?, protonated [M+H]⁺, lithiated [M+Li]⁺, sodiated [M+Na]⁺, and potassium‐cationized [M+K]⁺ ions. This allowed collision‐induced dissociation spectra of the ionized molecular ions to be obtained to give valuable structural information regarding the nature of both the glycoside and the aglycone moieties and the effect of metal cationization on the CID spectra. Glycosidic fission and ring cleavages of both aglycone and sugar moieties were the major fragmentation pathways observed during collision‐induced dissociation, where the losses of small molecules, the cinnamoyl and the cinnamate parts were also observed. Alkali metal cationization offers additional fragmentation pathways involving cross rings cleavage under CID conditions. Unlike the dissociation of protonated molecular ions, that of metal‐cationized molecules also provides sugar fragments where the C₀ ⁺ fragment corresponding with the glucose ion was obtained as a major daughter peak for all the studied compounds. Even with low abundance, fragment ions coordinated to K⁺ were also observed from [M+K]⁺.     

Near resonance charge transfer from a laser excited donor state

A laser induced charge transfer from Na(3p) to hydrogen-ions at different kinetic energies has been studied. An enhancement factor of about 90% in the production rate of Lyman-α radiation has been demonstrated to occur only with H⁺ and Na(3p) atoms reaction; no enhancement was observed with either H ₂ ⁺ or H ₃ ⁺ ions. Absolute cross-section for the production of Lyman-α radiation during the collision of H⁺, H ₂ ⁺ and H ₃ ⁺ ions and Na(3p) and Na(3s) atoms have been measured in the energy range 1–600eV. The charge exchange reactions involving hydrogen-ions and Na(3p) atoms created by two different methods have also been compared.     

Fragmentation of polyatomic ions produced by electron-loss collisions of butane and isobutane molecules with ions of kiloelectronvolt energy

Fragmentation accompanying the loss of electrons by butane and isobutane (C₄H₁₀) molecules in collisions with energy H⁺, He²⁺, and Ar⁶⁺ ions of kiloelectronvolt energies is studied. The electron density functional technique is applied to C _n H_2n+2 alkane molecules and their respective C _n H _2n+2 ⁺ ions to carry out quantum-chemical calculations of the atomic spacing, electron total energy for the initial configuration of the ionizing molecules and ions in the ground state, and atomic bond breaking energy necessary to produce different ion fragments. The fragmentation energy is correlated with the fragmentation probability. It is shown that the relative cross sections of ion fragmentation depend primarily on the related energy consumption. However, the process cross section is also strongly affected by the initial configuration of C₄H₁₀ isomer molecules, as well as by the amount of dangling and arising atomic bonds involved in the formation of each ion fragment.     

Collision-induced dissociation of H 2 + ions into the fragmentations H+H(2p) and H++H(2p)

Using a photon-particle delayed coincidence method the energy distributions of H +H(2p) and H⁺+H(2p) fragment pairs have been measured arising from collisional dissociation of 10 keV H ₂ ⁺ ions incident on various target gases. H fragments in their 2p state are identified by the Lymanα radiation emitted. The distribution of H+H(2p) fragment pairs arising from dissociative charge exchange reveals a sharp increase below 0.2 eV in the center-of-mass frame of the H ₂ ⁺ ion. This is ascribed to predissociation of vibrational levels of higher H₂ Rydberg states close above then=2 dissociation limit by those H₂ Rydberg states which separate into H+H(2p) fragments. Only direct transitions into the continuum of theGK ¹ ∑ _g ⁺ state may compete. Some structure at 0.3–0.5 eV is attributed to the three statesI ¹ П _g,i ³ П _g, andh ³ bE _g ⁺ having potential barriers of this height. The distributions for H⁺+H(2p) have maxima at 3.4, 3.8, and 4.2 eV for a H₂, Ar, and He target, respectively, indicating that the 2pπ _u state as well as the 3dσ _g state ofH ₂ ⁺ is excited. The H+H(2p) process has a greater probability than the H⁺+H(2p) process for Ar and H₂ targets, though all electronic H₂ states under consideration are bound.     

Collision-induced dissociation of H 3 + ions

For collision energies between 100 and 500 eV the collision induced dissociation of H ₃ ⁺ colliding with H₂, He and Kr gas targets was measured. We obtained total cross sections and angular distributions of the charged collision fragments for the main reaction channels. H ₃ ⁺ +H₂→H⁺+2H² and H ₃ ⁺ +H₂→H ₂ ⁺ +H₂+H. An analysis of the kinetics yields that the dissociation proceeds via vibrational-rotational excitation of H ₃ ⁺ by mutually induced dipolmoments.     

Mössbauer effect studies on alkali tris (malonato) ferrates(III)

Mössbauer spectra of alkali tris(malonato) ferrates(III) i.e. M₃[Fe(C₃H₂O₄)₃].4H₂O(M=Li, Na, K, NH₄) at 298±2K display a single broad absorption band due to spin lattice relaxation effect. The isomer shift values indicate these complexes to be high spin with octahedral symmetry. The isomer shift shows a decreasing trend with the increase in electronegativity/polarizing power of the substituent cation (Li⁺, Na⁺, K⁺, NH₄ ⁺). A linear correlation between isomer shift values and the (Fe-O) stretching freguencies has also been observed.     

Structure and magnetotransport properties of the new quasi-two-dimensional molecular metal β″-(BEDT-TTF)4H3O[Fe(C2O4)3] · C6H4Cl2

The β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G(A^I=NH ₄ ⁺ , H₃O⁺, K⁺, Rb⁺; M^III=Fe, Cr; G = “guest” solvent molecule) family of layered molecular conductors with magnetic metal oxalate anions exhibits a pronounced dependence of the conducting properties on the type of neutral solvent molecules introduced into the complex anion layer. A new organic dichlorobenzene (C₆H₄Cl₂)-containing conductor of this family, namely, β″-(BEDT-TTF)₄H₃O[Fe(C₂O₄)₃] · C₆H₄Cl₂, is synthesized. The structure of the synthesized single crystals studied by X-ray diffraction is characterized by the following parameters: a = 10.421(1) Å, b= 19.991(2) Å, c= 35.441(3) Å, β = 92.87(1)°, V= 7374(1) ų, space groupC2/c, and Z = 4. In the temperature range 0.5&;2-300 K, the conductivity of the crystals is metallic without changing into a superconducting state. The magnetotransport properties of the crystals are examined in magnetic fields up to 17 T at T = 0.5 K. In fields higher than 10 T, Shubnikov-de Haas oscillations are detected, and the Fourier spectrum of these oscillations contains two frequencies with maximum amplitudes of about 80 and 375 T. The experimental results are compared with the related data obtained for other phases of this family. The possible structural mechanisms of the effect of a guest solvent molecule on the transport properties of the β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G crystals are analyzed.     

Optical Properties of Solid Pseudoisocyanine Films Doped with Cluster Derivatives of Boron Hydrides

The formation and optical properties of J aggregates of pseudoisocyanine iodide in solid films in the presence of cluster anionic derivatives of boron hydrides and carboranes (B₁₀H ₁₀ ^2- , B₁₂H ₁₂ ^2- , B₂₀H ₁₈ ^2- , [Ni^IV(1,2-B₉C₂H₁₁)₂]⁰, 1,2-B₉C₂H ₁₂ ^- , [Co(1,2-B₉C₂H₁₁)₂]^-, [Ni(1,2-B₉C₂H₁₁)₂]^-, B₁₀H₈I ₂ ^2- , [Sn(1,2-B₉C₂H₁₁)]⁰) are studied. It is shown that the addition of anions B₁₀H ₁₀ ^2- or B₁₀H₈I ₂ ^2- leads to an efficient formation of stable J aggregates. The addition of carborane complex of nickel [Ni^IV (1,2-B₉C₂H₁₁)₂]⁰ also leads to the formation of J aggregates, although less stable ones. Carborane complex of tin [Sn^II(1,2-B₉C₂H₁₁)]⁰ facilitates the formation of a monomeric form of the dye. The remaining compounds yield no distinct pattern of formation of a certain monomeric or J-aggregated film structure. With the aid of the semiempirical AM1 method, the charge distributions in the cation of the dye and anionic derivatives of the boron hydrides are calculated. It is supposed that the bipolar distribution of a negative charge in the B₁₀H ₁₀ ^2- anion facilitates the formation of a J aggregate. By addition of salts of organic cations to a film of pseudoisocyanine-closo-hydrodecaborate (PCG), J aggregates with a narrow width of the J peak are obtained. The thermal decay of J aggregates in these films is studied. On the basis of the data obtained (the presence of an isosbestic point upon thermal decomposition of J aggregates and their reaggregation; the narrowing and increasing of the J absorption peak, as well as increasing of luminescence, upon dilution of a J-aggregated PCG film with organic cations; and the bipolar character of the electrostatic interaction of the B₁₀H ₁₀ ^2- anion with the dye), it is assumed that the J peak of pseudoisocyanine in the films studied corresponds to the absorption of a dimeric form of the dye.     

Ionization and dissociative ionization of methane molecules

A technique for mass-spectrometric investigation of the yield of positive ions produced by direct and electron-impact dissociative ionization of methane molecules is described, and respective experimental data are presented. Doubly charged C ₂ ⁺ , CH ₃ ²⁺ , and CH ₄ ²⁺ ions, as well as singly charged D ₂ ⁺ , CD ₃ ⁺ , and CD ₄ ⁺ ions, are detected in the mass spectrum of a methane molecule at electron energy U _e = 90 eV for the first time. From ionization efficiency curves, the ionization energy of the parent molecule and the appearance energy of fragment ions are determined. The ionization energy of the CH₄ molecule is found to be 12.62 ± 0.20 eV. Electron-molecular reactions that may take place when a low-energy electron beam interacts with a methane molecule are analyzed. The ionization process and the formation of methane molecule fragments are studied.     

[2.2.2]Paracyclophane as a receptor for the cesium cation in the gas phase

By using electrospray ionisation mass spectrometry, it was proven experimentally that the cesium cation (Cs⁺) forms with [2.2.2]paracyclophane (C₂₄H₂₄) the cationic complex [Cs(C₂₄H₂₄)]⁺. Further, applying quantum chemical calculations, the most probable structure of the [Cs(C₂₄H₂₄)]⁺ complex was derived. In the resulting complex with a symmetry very close to C₃, the ‘central’ cation Cs⁺, fully located in the cavity of the parent [2.2.2]paracyclophane ligand, is bound to all three benzene rings of [2.2.2]paracyclophane via cation–π interaction. Finally, the interaction energy, E(int), of the considered cation–π complex [Cs(C₂₄H₂₄)]⁺ was found to be ?73.2 kJ/mol, confirming the formation of this fascinating complex species as well. This means that [2.2.2]paracyclophane can be considered as a receptor for the Cs⁺ cation in the gas phase.     

Mechanistic studies of the photochemical nitration of phenols, 1,2-dimethoxybenzene and anisoles with tetranitromethane by15N CIDNP

During the photochemical nitration of phenol, 3,5-dimethylphenol and 1,2-dimethoxybenzene (8) with¹⁵N-enriched tetranitromethane, the¹⁵N nuclear magnetic resonance (NMR) signals of the nitro products 2-nitrophenol, 4-nitrophenol, 2-nitro-3,5-dimethylphenol, 4-nitro-3,5-dimethylphenol and 1,2-dimethoxy-4-nitrobenzene (9) appear in emission. The nuclear polarizations are built up in radical pairs formed by radical cations or in case of the phenols by phenoxyl radicals and^?NO₂. They are generated by photoreactions from excited triplet states of the reactants or by free radical encounters. With8, 1,2-dimethoxy-4-trinitromethylbenzene is also formed which slowly converts to9. In contrast to this, the¹⁵N NMR signals of the nitration products of anisole (11) and 3,5-dimethylanisole (12), 2-nitroanisole, 4-nitroanisole, 3,5-dimethyl-2-nitroanisole and 3,5-dimethyl-4-nitroanisole appear in enhanced absorption indicating the appearance of singlet radical pairs [11 ^+?,^?NO₂]^S and [12 ^+? ,^?NO₂]^S in which the nuclear polarizations are built up. The singlet radical pairs are formed by decomposition of an unstable intermediate, most probably a nitro-trinitromethyl adduct.     

Modeling of the molecular and electronic structures of multiple-decker sandwich macromolecules with η5-π bonds on the basis of biscyclopentadienyl derivatives 60H10 of a C60 fullerene

The molecular and electronic structures of the (CpFe)₂C₆₀H₁₀ complex of the D _5d symmetry, where Cp is the $^ \cdot C_5 H_5 $ cyclopentadienyl radical, are simulated using the ab initio Hartree-Fock-Roothaan method in the 3–21G basis set. In this complex, hydrogen atoms are attached to carbon atoms of the C₆₀ fullerene which occupy α-positions with respect to two oppositely lying five-membered rings. Each FeCp semisandwich moiety is linked to atoms of one of these five-membered rings by the η⁵-π-type bond. It is found that the energy of the η⁵-π Fe-C₆₀H₁₀ bonds in the (CpFe)₂C₆₀H₁₀ complex is comparable to that of the η⁵-π Fe-Cp bond in the FeCp₂ ferrocene molecule. The optimum geometry calculated for the (CpFe)₂C₆₀H₁₀ complex is used for modeling of the structure of the quasi-linear macromolecule [-FeC₆₀H₁₀-]_n, (I). The band structure of the energy spectrum of macromolecule I is calculated in the valence approximation of the extended Hückel method within the crystalline-orbital approach. The band gap in the spectrum of macromolecule I is ～2.27 eV. The band structure of the spectrum of this macromolecule is compared with the spectra of the hypothetical molecules [-FeCp-]_n and [-FeC₂₀-]_n.     

Structure of some FeII − III hydroxysalt green rusts (carbonate, oxalate, methanoate) from Mössbauer spectroscopy

The abundances of Fe^II and Fe^III environments within green rusts one, GR1s, that intercalate carbonate, oxalate and methanoate (formate) anions are found from Mössbauer spectra for compositions corresponding to [Fe $^{\rm II}_{6}$ Fe $^{\rm III}_{2}$ (OH)₁₆]^2?+??[CO $_{3}^{2-}$ ?5H₂O]^2???, [Fe $^{\rm II}_{4}$ Fe $^{\rm III}_{2}$ (OH)₁₂]^2?+??[CO $_{3}^{2-}$ ?3H₂O]^2???, [Fe $^{\rm II}_{6}$ Fe $^{\rm III}_{2}$ (OH)₁₆]^2?+??[C₂O $_{4}^{2-}$ ?4H₂O]^2??? and [Fe $^{\rm II}_{5}$ Fe $^{\rm III}_{2}$ (OH)₁₄]^2?+??[2HCOO^????3H₂O]^2???. These formulae correspond to orders α, β and γ where cation distances are (2 × a ₀), ( $\surd 3$ × a ₀) or a mixture of both leading to (7 × a ₀), where ratio x = {[Fe^III]/[Fe_total]} = 1/4, 1/3 and 2/7, respectively. Anion distributions within interlayers are also devised and long-range orders determined accordingly.     

Assessment of the nature of interactions of cations with cycloheptatriene derivatives using change in the aromaticity: Comparison with electron density and NBO results

ABSTRACT

Interactions of cycloheptatriene derivatives, C₇H₆X, (X?=?NH, PH, AsH, O, S, Se) with the cations H⁺, CH₃⁺, Cu⁺, Al⁺, Li⁺, Na⁺, and K⁺ are studied using B3LYP functional and 6-311++G(d,p) basis set. The calculated gas-phase cation affinities (CA) and cation basicities (CB) for all molecules decrease as H⁺ > CH₃⁺ > Cu⁺ > Al⁺ > Li⁺ > Na⁺ > K⁺. We used the induced aromaticity in the 7-membered ring of C₇H₆X upon interaction with the cations, M⁺, as a measure of C₇H₆X/M⁺ interaction. Nucleus-independent chemical shift (NICS) and harmonic oscillator model of aromaticity (HOMA) were used as two indices of aromaticity. The highest and lowest induced aromaticities were observed for interactions of H⁺ and K⁺, respectively. Also, the aromaticity induced by interaction with a cation in C₇H₆AsH and C₇H₆PH was larger than that in C₇H₆NH and C₇H₆O. Hence, the aromaticity was considered as a measure of covalency for the C₇H₆X/M⁺ interactions showing a rational dependence on both the molecule and cation. The nature of the interactions was also assessed using electron density, charge distribution analysis and NBO calculations. The results of the aromaticity indices, NICS and HOMA, were compared with the electron density and NBO results.     

Time evolution of the Infrared Laser Induced Breakdown Spectroscopy of DNA bases Guanine and Adenine

Laser-Induced Breakdown Spectroscopy (LIBS) of DNA bases Guanine and Adenine was studied using a high-power CO₂ pulsed laser (λ=10.591 μm, τ _FWHM=64 ns and fluences ranging from 25 to 70 J/cm²). The strong emission of the adenine and guanine plasma, collected using a high-resolution spectrometer, at medium-vacuum conditions (4 Pa) and at 1 mm from the target, exhibits excited molecular bands of CN (B² Σ ⁺–X² Σ ⁺) and excited neutral H and ionized N⁺ and C⁺. The medium-weak emission is due to excited species C²⁺, C³⁺, N, O, O⁺, O²⁺ and molecular band systems of $\mathrm{C}_{2}(\mathrm{d}^{3}\varPi_{\mathrm{g}}\mbox{--}\mathrm{a}^{3}\varPi_{\mathrm{u}};\ \mathrm{D}^{1}\varSigma_{\mathrm{u}}^{+}\mbox{--}\mathrm{X}^{1}\varSigma_{\mathrm{g}}^{+})$ , OH(A² Σ ⁺–X² Π), NH(A³ Π–X³ Σ ^?), CH(A² Π–X² Π), $\mathrm{N}_{2}^{+}(\mathrm{B}^{2}\varSigma_{\mathrm{u}}^{+}\mbox{--} \mathrm{X}^{2}\varSigma_{\mathrm{g}}^{+})$ and N₂(C³ Π _u–B³ Π _g). We focus our attention on the temporal evolution of different atomic/ionic and molecular species. The velocity distributions for various (different) species were obtained from time-of-flight (TOF) measurements. Intensities of some lines from C⁺ were used for determining electron temperature and their Stark-broadened profiles were employed to estimate the temporal evolution of electron density.     

Energy spectra and energy correlations in the decayH→ZZ→μ+μ−μ+μ−

It is shown that in the sequential decay $H \to ZZ \to (f_1 \bar f_1 ) + (f_2 \bar f_2 )$ , the energy distribution of the final state particles provides a simple and powerful test of theHZZ vertex. For a standard Higgs boson, the energy spectrum of any final fermion, in the rest frame ofH, is predicted to be dΓ/dx～1+β⁴?2(x?1)², with $\beta = \sqrt {1 - 4m_Z^2 /m_H^2 } $ and 1?β≤x=4E/m _H ≤1+β. By contrast, the spectrum for a pseudoscalar Higgs is dΓ/dx～β²+(x?1)². There are characteristic energy correlations betweenf ₁ andf ₂ and betweenf ₁ andf ₂. These considerations are applied to the “gold-plated” reactionH→ZZ→μ⁺μ^?μ⁺μ^?, including possible effects ofCP-violation in theHZZ coupling. Our formalism also yields the energy spectra and correlations of leptons in the decay $H \to W^ + W^ - \to l^ + v_l l^ - \bar v_l $ .     

Ultrafast delocalization of hydrogen atoms in allene in intense laser fields

Ultrafast delocalization of hydrogen atoms in allene (CH₂=C=CH₂) induced by intense laser fields was investigated by the Coulomb explosion coincidence momentum imaging method. On the basis of the kinetic energy distributions of the fragment ions produced through the two three-body Coulomb explosion pathways, C₃H₄³⁺ ? H⁺ + CH⁺ + C₂H₂⁺\mathrm{C}_{3}\mathrm{H}_{4}^{3+} \rightarrow \mathrm{H}^{+} + \mathrm{CH}^{+} + \mathrm{C}_{2}\mathrm{H}_{2}^{+} and C₃H₄³⁺ ? H⁺ + C₂H⁺ +CH₂⁺\mathrm{C}_{3}\mathrm{H}_{4}^{3+} \rightarrow \mathrm{H}^{+} + \mathrm{C}_{2}\mathrm{H}^{+} +\mathrm{CH}_{2}^{+}, and the proton maps for both pathways, it was shown that the decomposition proceeds in a stepwise manner as well as in a concerted manner. The time scale of the hydrogen migration within an allene molecule was estimated to be ∼20 fs.     

Nambu sum rule in the NJL Models: from superfluidity to top quark condensation

It may appear that the recently found resonance at 125 GeV is not the only Higgs boson. We point out the possibility that the Higgs bosons appear in models of top-quark condensation, where the masses of the bosonic excitations are related to the top quark mass by the sum rule similar to the Nambu sum rule of the NJL models [1]. This rule was originally considered by Nambu for superfluid ³He-B and for the BCS model of superconductivity. It relates the two masses of bosonic excitations existing in each channel of Cooper pairing to the fermion mass. An example of the Nambu partners is provided by the amplitude and the phase modes in the BCS model describing Cooper pairing in the s-wave channel. This sum rule suggests the existence of the Nambu partners for the 125 GeV Higgs boson. Their masses can be predicted by the Nambu sum rule under certain circumstances. For example, if there are only two states in the given channel, the mass of the Nambu partner is ～ 325 GeV. They together satisfy the Nambu sum rule M ₁ ² + M ₂ ² = 4M _t ² , where M _t ～ 174 GeV is the mass of the top quark. If there are two doubly degenerated states, then the second mass is ～210 GeV. In this case the Nambu sum rule is 2M ₁ ² + 2M ₂ ² = 4M _t ² . In addition, the properties of the Higgs modes in superfluid ³He-A, where the symmetry breaking is similar to that of the Standard Model of particle physics, suggest the existence of two electrically charged Higgs particles with masses around 245 GeV, which together also obey the Nambu sum rule M ₊ ² + M _? ² = 4M _t ² .