Structures and reactions of biomolecular ions produced with electrospray ionization

Photo-induced reaction of [Fe(III)-protoporphyrin]⁺ (hemin⁺) ions solvated with dimethylsulfoxide (DMSO) is investigated by using a tandem mass spectrometer with electrospray ionization. We measure the photodissociation yields of mass-selected hemin⁺(DMSO)_n clusters for n = 0-3. The mass spectra of the fragment ions show the -cleavage of carboxymethyl groups in addition to the evaporation of solvent molecules. Yield of the -cleavage reaction is found to depend strongly on the excitation energy and the number of solvent molecules. We also examine photo-induced reactions of multiply-charged cytochrome c ions, (M + nH)^{n +} ( n = 9-17). Photoionization is found to be the dominant process for the lower charged states ( n = 9-12) and its yield decreases rapidly with increasing the charge. The photoionization is ascribed to the emission of electron by multiphoton excitation of heme under the influence of Coulomb attractive potential arising from the charges in the polypeptide chain. Model calculations of the Coulomb potential suggest that the structure of the polypeptide chain is completely elongated.     

Structures and reactions of hydrated biomolecular cluster ions

Photo-induced reactions and metastable decompositions of cluster ions containing glycine, tryptophan, tryptophanylglicine and [Fe(III)-protoporphyrin]⁺ (hemin⁺) ions solvated with water molecules are studied with electrospray ionization (ESI). The ESI ion source is improved to produce hydrated biomolecular cluster ions. Metastable decompositions of the hydrated clusters following primary mass selection are measured to determine the incremental solvent binding energies for the clusters by using evaporative ensemble model. From these experimental findings, stability of the cluster ions is discussed in terms of delocalization of ionic charges. We also measure the photodissociation yields of mass-selected water clusters containing hemin⁺ ions at 355 and 532 nm. The mass spectra of photofragments show the β-cleavage of carboxymethyl groups in addition to the evaporation of solvent molecules.     

SiC bonding in ( C 60 ) n Si m clusters

This paper deals with a new type of SiC bonding where silicon atom seems to bridge C₆₀ molecules. We have studied films obtained by deposition of (C₆₀)_nSi_m clusters prepared in a laser vaporization source. Prior deposition, free ionized clusters were studied in a time-of-flight mass spectrometer. Mixed clusters (C₆₀)_nSi_m were clearly observed. Abundance and photofragmentation mass spectroscopies revealed the relatively high stability of the (C₆₀)_nSi _n ⁺ , (C₆₀)_nSi _{n - 1} ⁺ and (C₆₀)_nSi _{n - 2} ⁺ species. This observation is in favor of the arrangement of these complexes as polymers where the C₆₀ cages may be bridged by a silicon atom. Free neutral clusters are then deposited onto substrate making up a nanogranular thin film (≃ 100 nm). The film is probed by Auger and X-ray photoemission spectroscopies, but above all by surface enhanced Raman scattering. The results suggest an unusual chemical bonding between silicon and carbon and the environment of the silicon atom is expected to be totally different from the sp³ lattice: ten or twelve carbon neighbors might surround silicon atom. The bonding is discussed to the light of the so-called fullerene polymerization as observed for pure fullerite upon laser irradiation. This opens a new route for bridging C₆₀ molecules together with an appreciable energy bonding, since the usual van der Waals bonding in fullerite could be replaced by an ionocovalent bond. Such an assumption must be checked in the future by XAS and EXAFS experiments. Received 15 November 2000     

幻数尺寸Li-n-1,Lin,Li+ n+1(n=20,40)团簇的几何结构、电子与光学性质的第一性原理研究

基于密度泛函理论,采用第一性原理分子动力学模拟退火方法,对Li^-_n-1,Li_n,Li⁺_n+1 (n=20,40)的最低能量结构进行了全局搜索. 发现锂团簇的生长模式是以单个或多个嵌套的正多面体为核心,其余原子以五角锥为基本单元围绕核心生长. 基于最低能量结构的第一性原理电子结构计算得到锂团簇的分子轨道能级分布与无结构凝胶模型给出的电子壳层完全一致. 在总电 关键词： 团簇 电子结构 极化率 光吸收     

Hydrogenated carbon clusters produced by highly charged ion impact on solid

The emission of small (hydrogenated) carbon cluster ions C_nHm ⁺ (n =2-22) upon highly charged Xe^q+ (q =20-44) impact on C₈₄ surfaces is studied by means of time-of-flight secondary ion mass spectrometry. The respective stage of hydrogenation/protonation of a certain carbon cluster ion Cn ⁺ is a strong indication for its geometrical structure. From the cluster ion yield as a function of cluster size it can be concluded, that the hydrogenation takes place after the initial carbon cluster formation. The carbon clusters seem to be emitted as an entity in agreement with “equilibrium” and “shock wave” models. Received 4 February 2000     

Reactions induced in (CF3I) n clusters by femtosecond UV laser pulses

The excitation and ionization of CF₃I molecules and their clusters by femtosecond UV laser pulses is studied. It is concluded that the types of excitation of free CF₃I molecules and their clusters by femtosecond UV laser pulses are different. The composition and kinetic energy of ion products observed upon the ionization of (CF₃I) _n clusters by femtosecond pulses are found to differ considerably from those obtained upon ionization by nanosecond pulses. It is shown that the molecular I ₂ ⁺ ion is produced in reactions induced in (CF₃I) _n clusters by UV radiation. Using the pump-probe method, we found the two channels of producing I ₂ ⁺ ions with characteristic times ??₁ ?? 1 ps and ??₂ ?? 7 ps. A model of the reactions under study proposed in the paper is consistent with our experimental results.     

Interaction between aromatic amine cations and nonpolar solvents: Infrared spectra of isomeric aniline -Ar n ( ) complexes

Infrared (IR) photodissociation spectra of the aniline⁺-Ar_n cations, An ⁺ - Ar _n (n = 1, 2), are analyzed in the vicinity of the N-H stretch fundamentals. The complexes are produced in an electron impact (EI) ion source which produces predominantly the most stable cluster isomers. Two isomers of An⁺-Ar are identified by their characteristic N-H stretch frequencies: the planar proton-bound global minimum, in which the Ar ligand forms a nearly linear H-bond to the amino group, and the less stable π-bound local minimum, in which the Ar atom is attached to the π-electron system of the aromatic ring. This result is the first unambiguous detection of the most stable H-bound An⁺-Ar dimer. All previous spectroscopic studies of An⁺-Ar employed resonance enhanced multiphoton ionization (REMPI) of neutral An-Ar and identified only the less stable π-bound cation due to restrictions arising from the Franck-Condon principle. The EI-IR spectrum of An⁺-Ar₂ shows that the most stable structure of this trimer features two equivalent H-bonds (C_2v symmetry). The interpretation of the experimental data is supported by quantum chemical calculations. The ab initio potential of An⁺-Ar calculated at the UMP2/6-311G(2df, 2pd) level features H-bound global minima ( D _e = 513 cm^-1) and π-bound local minima ( D _e = 454 cm^-1), with a barrier of V _b ≈ 140 cm^-1 for isomerization from the π-bound toward the H-bound minimum. Received 4 February 2002 Published online 13 September 2002     

(CH3I)n(n=1,2,3,4)的同步辐射光电离研究

用VUV同步辐射辐照在连续的超声射流冷却束中产生的（CH₃I)_n（n=1,2，3，4）团簇分子，通过测量其光电离及解离电离产生的各种离子的光电离效率（PIE）曲线，获得了（CH₃I)_n⁺（n=1，2，3，4）的绝热电离势及各种碎片离子的出现势，估算了有关分子的键能．在CH₃I⁺的PIＥ曲线上观察到CH₃I分子的自电离结构，并对其进行了标识，归属为收敛于CH₃I⁺（²E_1/2）态的4组Rydberg系，即ns，npσ，npπ和nd． 关键词：     

Microscopic structure of liquid dimethyl sulphoxide and its electrolyte solutions: molecular dynamics simulations

Molecular dynamics (MD) simulations of pure dimethyl sulphoxide (DMSO) and solutions of Na⁺, Ca²⁺, Cl^?, NaCl and CaCl₂ in DMSO have been performed at 298.15 K and 398.15 K in NVT ensembles by using a four-interaction-site model of DMSO and reaction field method for Coulombic interactions. The structure of solvent, ion-solvation shells and ion-pairs have been analysed by employing a concept of coordination centres and characteristic vectors of the solvent molecule. Results are given for atom-atom (corresponding to DMSO), ion-atom and ion-ion radial distribution functions (RDFs), orientation of the DMSO molecules and their geometrical arrangements in the first solvation shells of the ions (Na⁺, Ca²⁺, Cl^?). A preferential formation of cyclic dimers with antiparallel alignment between dipole moments of nearest-neighbour molecules in the pure solvent is found. Geometrical models of the first coordination shells of the ions in ‘infinitely dilute solutions’ are proposed. Ion-ion RDFs in NaCl-DMSO and CaCl₂-DMSO solutions reveal the presence of both solvent separated (SSIP) and contact (CIP) ion pairs. The structures of the solvation shells of such ion pairs are also discussed.     

Direct observation of intracluster reactions induced in (CF<Subscript>3</Subscript>I)<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> clusters by femtosecond ultraviolet radiation

Intracluster reactions that are induced in (CF₃I) _n clusters by femtosecond ultraviolet radiation, including the reaction of the formation of the I₂⁺ molecular ion, have been directly observed. It has been shown that there are two channels of the formation of I₂⁺ ions with the characteristic times τ₁ ≈ 1 ps and τ₂ ≈ 7 ps. A model of these reactions has been proposed that is in good agreement with the experimental data.     

Sputtering of AlxGa1−x As semiconductor targets by Ar+ ions with energies of 2–14 keV

Investigations of the sputtering of Al_xGa_1−x As semiconductor solid solutions by Ar⁺ ions with energies of 2–14 keV are performed. The dependence of the sputtering yield on the energy and angle of incidence of the ions are determined and the character of the surface relief formed during the sputtering is investigated. A comparison with theory shows that the best agreement between theory and experiment is achieved when the Haff-Switkowski formula is used together with Yudin’s stopping cross section. It is shown that the surface binding energies obtained differ from the atomization energies by an amount approximately equal to the amorphization energy. Zh. Tekh. Fiz. 67, 113–117 (June 1997)     

Improvement of the Applicability, Efficiency, andPrecision of the Penning Trap Mass Spectrometer ISOLTRAP

With the Penning trap mass spectrometer ISOLTRAP, close to 200 nuclides have already been investigated and their masses determined with a typical relative precision of δm/m=10⁻⁷. Recently, ISOLTRAP's beam preparation system was replaced by an RFQ ion beam cooler and buncher. The principle and the characteristics of this new beam preparation system will be presented. It is planned to use ions of various carbon clusters C⁺ _n (n>1) as reference ions for mass measurements. Apart from negligible molecular binding energies, these clusters have masses that are exact multiples of the unified atomic mass unit. This will allow ISOLTRAP to carry out absolute mass measurements as well as to investigate possible mass-dependent systematic errors. The results of tests of the production, transport, and trapping of such carbon clusters will be presented. This revised version was published online in July 2006 with corrections to the Cover Date.     

Balmer Hβ vs. Dβ line intensity in the collisions of H+, H2 +, H3 +, D+, D2 +, and D3 + ions with “realistic” metal surface at energies below 1 keV

The intensities of hydrogen H_β and deuterium D_β spectral lines of the Balmer series were measured as a function of collision energy when H⁺, H₂ ⁺, H₃ ⁺, D⁺, D₂ ⁺, and D₃ ⁺ ions impinged on Al, Ti, Cu, Mo, W, and Pb targets. The collision energies were kept in the 100–1000 eV range. The target surface was contaminated with hydrocarbons from the vacuum pumping system and possibly also by oxygen molecules due to limited vacuum conditions. At projectile velocities above 200 km/s the luminescence of backscattered deuterium atoms is about 30–50% weaker than that of hydrogen atoms.     

The structures and stabilities of mixed inert gas cluster ions: NeHe+ n and ArHe+ n

DIM-type matrices for RgHe⁺ _n clusters have been established from the results of ab initio calculations on RgHe and RgHe⁺ (Rg = Ne and Ar). The method has been tested against ab initio calculations on linear and T shaped RgHe⁺ ₂ and found to be satisfactory. Rotational invariance has been established for larger clusters, and the geometries and energies of clusters up to n = 16 have been determined. Ne cluster ions are more stable than Ar cluster ions because of the greater contribution from charge transfer, and are structurally different. The relative stabilities of these cluster ions are consistent with the available experimental data.     

Exclusive charge exchange reaction pD↦n(pp) within the Bethe-Salpeter formalism

The exclusive charge exchange reaction pD↦n(pp) at intermediate and high energies is studied within the Bethe-Salpeter formalism. The final-state interaction in the detected pp pair at nearly zero excitation energy is described by the ¹ S ₀ component of the Bethe-Salpeter amplitude. Results of numerical calculations of polarization observables and differential cross-section persuade that, as in the non-relativistic case, this reaction i) can be utilized as a “relativistic deuteron polarimeter” and ii) delivers further information about the elementary nucleon-nucleon charge exchange amplitude. Received: 26 November 2002 / Accepted: 30 January 2003 / Published online: 29 April 2003     

Electron multiplicity in slow collisions of Ar ions with C

Electron capture by Ar⁸⁺ in collisions with C₆₀ fullerene has been investigated using coincident measurements of the number n of ejected electrons, the mass and charge of multicharged Cr+ ₆₀ recoil ions and their fragments Ci+ m and the final charge state of outgoing projectiles Ar(8-s)+ (). The number of captured electrons r is the sum of the numbers of stabilized and emitted electrons: r = n + s. The ratio n / s decreases by a factor three with s increasing from 1 to 7 showing that the multiply excited states populated by capture of a large number of electrons are rather stable against auto-ionisation. Each kinetic energy spectrum of Ar⁺ and Ar²⁺ projectiles is composed of two peaks which we attribute to collisions “inside” and “outside” the C₆₀ cage. The measured energy shift of the projectile keV is consistent with the corresponding energy loss keV in a carbon foil with an equivalent thickness. Inside collisions are characterized by a strong dissociation of recoil ions into light monocharged fragments and by a high multiplicity of ejected electrons. Received: 25 March 1998 / Received in final form and Accepted: 9 June 1998     

Collision-induced fragmentation and neutralization of methanol cluster cations

This contribution addresses the inelastic interaction of positively charged molecular cluster ions with a solid surface at kinetic energies up to 30 eV/molecule. We report experimental results on the scattering of mass-selected, protonated methanol cluster cations (CH₃OH)_nH⁺, n = 4-32, off a diamond-coated silicon surface. In particular we provide fragment size distributions of methanol cluster ions following their impact on the target, as well as surface-induced neutralization probabilities of methanol cluster ions as a function of the size and the kinetic energy of the parent clusters. Received 30 November 2000     

Carbon-cluster mass calibration at SHIPTRAP

A carbon-cluster ion source has been installed and tested at SHIPTRAP, the Penning-trap mass spectrometer for precision mass measurements of heavy elements at GSI. Carbon-cluster ions ¹²C_n ⁺, 5 ≤n ≤23, were produced by laser-induced desorption and ionization from a carbon sample. They were tested for the first time as reference ions in an on-line mass measurement of the radionuclides ¹⁴⁴Dy, ¹⁴⁶Dy and ¹⁴⁷Ho. In addition, carbon clusters of various sizes were used for an investigation of the systematic uncertainty of SHIPTRAP covering a mass range from 84 u to 240 u. The mass-dependent uncertainty was found to be negligible for the case of (m-m _ref)< 100 u. However, a systematic uncertainty of 4.5 ×10^-8 was revealed.     

Interaction of Pd cluster anions (Pdn -, n < 11) with oxygen

Interactions between oxygen and Pd cluster anions were studied using Time-of-Flight (ToF) mass spectrometry and Ultraviolet Photoelectron Spectroscopy (UPS). In contrast to the coinage metal clusters, no pronounced size selectivity towards chemisorption of oxygen molecules can be observed for the Pd cluster anions: regardless of the cluster size, no more than 2 oxygen molecules can be attached to a cluster. When Pd_nO_m ^- clusters are prepared by pre-dissociation of oxygen molecules by electric arc and post-reaction with Pd, the proportion of Pd cluster anions reacted with oxygen does not much change compared to the case of the reaction between Pd cluster anions and O₂ molecules. This result indicates that the O₂ chemisorption on Pd cluster anions does not involve large activations barriers: using different synthesis method of a cluster, one can get a better insight into the chemisorption routes of molecules on metal clusters.     

Negative ion photoelectron spectroscopy of 2,2’-bithiophene cluster anions, (2T)n - (n = 1–100)

Cluster anions of 2,2’-bithiophene, (2T)_n^-, were produced up to n ∼500 in the gas-phase. The energetics of the excess electron in the (2T)_n^- clusters with n =1-100 were explored by negative ion photoelectron spectroscopy. When the vertical detachment energies (VDEs) obtained from the photoelectron spectra were analyzed by a plot against n^-1/3, it has been revealed that the excess electron trapping level thus extrapolated is located at ∼0.8 eV below the conduction band minimum (i.e. LUMO) of the 2T thin film. The large slope of the VDEs vs. n^-1/3 plot suggests that the neutral 2T molecules surrounding the anion core take non-planar twisted conformations with permanent dipole moments, resulting in the exceedingly deep trapping of the excess electron in the 2T cluster anions.