Single photon ionization of van der Waals clusters with a soft x-ray laser: (SO2)n and (SO2)n(H2O)m

van der Waals cluster (SO2)n is investigated by using single photon ionization of a 26.5 eV soft x-ray laser. During the ionization process, neutral clusters suffer a small fragmentation because almost all energy is taken away by the photoelectron and a small part of the photon energy is deposited into the (SO2)n cluster. The distribution of (SO2)n clusters decreases roughly exponentially with increasing cluster size. The photoionization dissociation fraction of I[(SO2)(n-1)SO+] / I[(SO2)n+] decreases with increasing cluster size due to the formation of cluster. The metastable dissociation rate constants of (SO2)n+ are measured in the range of (0.6-1.5) x 10(4) s(-1) for cluster sizes 5< or =n< or =16. Mixed SO2-H2O clusters are studied at different experimental conditions. At the condition of high SO2 concentration (20% SO2 partial pressure), (SO2)n+ cluster ions dominate the mass spectrum, and the unprotonated mixed cluster ions (SO2)nH2O+ (1< or =n< or =5) are observed. At the condition of low SO2 concentration (5% SO2 partial pressure) (H2O)nH+ cluster ions are the dominant signals, and protonated cluster ions (SO2)(H2O)nH+ are observed. The mixed clusters, containing only one SO2 or H2O molecule, SO2(H2O)nH+ and (SO2)nH2O+ are observed, respectively.     

Single photon ionization of hydrogen bonded clusters with a soft x-ray laser: (HCOOH)x and (HCOOH)y(H2O)z

Pure, neutral formic acid (HCOOH)n+1 clusters and mixed (HCOOH)(H2O) clusters are investigated employing time of flight mass spectroscopy and single photon ionization at 26.5 eV using a very compact, capillary discharge, soft x-ray laser. During the ionization process, neutral clusters suffer little fragmentation because almost all excess energy above the vertical ionization energy is taken away by the photoelectron, leaving only a small part of the photon energy deposited into the (HCOOH)n+1+ cluster. The vertical ionization energy minus the adiabatic ionization energy is enough excess energy in the clusters to surmount the proton transfer energy barrier and induce the reaction (HCOOH)n+1+-->(HCOOH)nH+ +HCOO making the protonated (HCOOH)nH+ series dominant in all data obtained. The distribution of pure (HCOOH)nH+ clusters is dependent on experimental conditions. Under certain conditions, a magic number is found at n=5. Metastable dissociation rate constants of (HCOOH)nH+ are measured in the range (0.1-0.8)x10(4) s(-1) for cluster sizes 4相似文献   

Vacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters

In this work, we report on the vacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters. Clusters of methanol with water are generated via co-expansion of the gas phase constituents in a continuous supersonic jet expansion of methanol and water seeded in Ar. The resulting clusters are investigated by single photon ionization with tunable vacuum-ultraviolet synchrotron radiation and mass analyzed using reflectron mass spectrometry. Protonated methanol clusters of the form (CH3OH)nH(+) (n = 1-12) dominate the mass spectrum below the ionization energy of the methanol monomer. With an increase in water concentration, small amounts of mixed clusters of the form (CH3OH)n(H2O)H(+) (n = 2-11) are detected. The only unprotonated species observed in this work are the methanol monomer and dimer. Appearance energies are obtained from the photoionization efficiency (PIE) curves for CH3OH(+), (CH3OH)2(+), (CH3OH)nH(+) (n = 1-9), and (CH3OH)n(H2O)H(+) (n = 2-9) as a function of photon energy. With an increase in the water content in the molecular beam, there is an enhancement of photoionization intensity for the methanol dimer and protonated methanol monomer at threshold. These results are compared and contrasted to previous experimental observations.     

Dynamics and fragmentation of van der Waals clusters: (H2O)n, (CH3OH)n, and (NH3)n upon ionization by a 26.5 eV soft x-ray laser

A tabletop soft x-ray laser is applied for the first time as a high energy photon source for chemical dynamics experiments in the study of water, methanol, and ammonia clusters through time of flight mass spectroscopy. The 26.5 eV/photon laser (pulse time duration of approximately 1 ns) is employed as a single photon ionization source for the detection of these clusters. Only a small fraction of the photon energy is deposited in the cluster for metastable dissociation of cluster ions, and most of it is removed by the ejected electron. Protonated water, methanol, and ammonia clusters dominate the cluster mass spectra. Unprotonated ammonia clusters are observed in the protonated cluster ion size range 2< or =n< or =22. The unimolecular dissociation rate constants for reactions involving loss of one neutral molecule are calculated to be (0.6-2.7)x10(4), (3.6-6.0)x10(3), and (0.8-2.0)x10(4) s(-1) for the protonated water (9< or =n< or =24), methanol (5< or =n< or =10), and ammonia (5< or =n< or =18) clusters, respectively. The temperatures of the neutral clusters are estimated to be between 40 and 200 K for water clusters (10< or =n< or =21), and 50-100 K for methanol clusters (6< or =n< or =10). Products with losses of up to five H atoms are observed in the mass spectrum of the neutral ammonia dimer. Large ammonia clusters (NH(3))(n) (n>3) do not lose more than three H atoms in the photoionization/photodissociation process. For all three cluster systems studied, single photon ionization with a 26.5 eV photon yields near threshold ionization. The temperature of these three cluster systems increases with increasing cluster size over the above-indicated ranges.     

Protonation and Dehydrogenation During the Multiphoton Ionization of the Cluster: C_4H_5N(H_2O)_n

Proton transfer process in hydrogen-bonded clusters has attracted great interest of many chemists in physical chemistry and biochemistry1-5. Pyrrole (C4H5N) is one of the building blocks of some important biomolecules6. And pyrrole is a compound of five-membered hetero-cyclic aromatic ring, in which a lone pair of electrons offered by the N atom and the two double bonds form a delocalized big ( bond. In this paper we report on the observations for the cluster system pyrrole-water by use of a…     

Vacuum ultraviolet (VUV) photoionization of small water clusters

Tunable vacuum ultraviolet (VUV) photoionization studies of water clusters are performed using 10-14 eV synchrotron radiation and analyzed by reflectron time-of-flight (TOF) mass spectrometry. Photoionization efficiency (PIE) curves for protonated water clusters (H2O)(n)H+ are measured with 50 meV energy resolution. The appearance energies of a series of protonated water clusters are determined from the photoionization threshold for clusters composed of up to 79 molecules. These appearance energies represent an upper limit of the adiabatic ionization energy of the corresponding parent neutral water cluster in the supersonic molecular beam. The experimental results show a sharp drop in the appearance energy for the small neutral water clusters (from 12.62 +/- 0.05 to 10.94 +/- 0.06 eV, for H2O and (H2O)4, respectively), followed by a gradual decrease for clusters up to (H2O)23 converging to a value of 10.6 eV (+/-0.2 eV). The dissociation energy to remove a water molecule from the corresponding neutral water cluster is derived through thermodynamic cycles utilizing the dissociation energies of protonated water clusters reported previously in the literature. The experimental results show a gradual decrease of the dissociation energy for removal of one water molecule for small neutral water clusters (3 相似文献   

Hypoiodous acid as guest molecule in protonated water clusters: a combined FT-ICR/DFT study of I(H2O)n+.

Cationic water clusters containing iodine, of the composition I(H2O)n+, n = 0-25, are generated in a laser vaporization source and investigated by FT-ICR mass spectrometry. An investigation of blackbody radiation-induced fragmentation of size-selected clusters I(H2O)n+, n = 3-15, under collision-free conditions revealed an overall linear increase of the unimolecular rate constant with cluster size, similar to what has been observed previously for other hydrated ions. Above a certain critical size, I(H2O)n+, n greater than or approx. 13, reacts with HCl by formation of the interhalide ICl and a protonated water cluster, which is the reverse of a known solution-phase reaction. Accompanying density functional calculations illustrate the conceptual differences between cationic and anionic iodine-water clusters I(H2O)n+/-. While I-(H2O)n is genuinely a hydrated iodide ion, the cationic closed-shell species I(H2O)n+ may be best viewed as a protonated water cluster, in which one water molecule is replaced by hypoiodous acid. In the strongly acidic environment, HOI is protonated because of its high proton affinity. However, similar to the well-known H3O+/H5O2+ controversy in protonated water clusters, a smooth transition between H2IO+ and H4IO2+ as core ions is observed for different cluster sizes.     

Ionization induced relaxation in solvation structure: a comparison between Na(H2O)n and Na(NH3)n

The constant ionization potential for hydrated sodium clusters Na(H2O)n just beyond n=4, as observed in photoionization experiments, has long been a puzzle in violation of the well-known (n+1)(-1/3) rule that governs the gradual transition in properties from clusters to the bulk. Based on first principles calculations, a link is identified between this puzzle and an important process in solution: the reorganization of the solvation structure after the removal of a charged particle. Na(H2O)n is a prototypical system with a solvated electron coexisting with a solvated sodium ion, and the cluster structure is determined by a balance among three factors: solute-solvent (Na+-H2O), solvent-solvent (H2O-H2O), and electron-solvent (OH{e}HO) interactions. Upon the removal of an electron by photoionization, extensive structural reorganization is induced to reorient OH{e}HO features in the neutral Na(H2O)n for better Na+-H2O and H2O-H2O interactions in the cationic Na+(H2O)n. The large amount of energy released, often reaching 1 eV or more, indicates that experimentally measured ion signals actually come from autoionization via vertical excitation to high Rydberg states below the vertical ionization potential, which induces extensive structural reorganization and the loss of a few solvent molecules. It provides a coherent explanation for all the peculiar features in the ionization experiments, not only for Na(H2O)n but also for Li(H2O)n and Cs(H2O)n. In addition, the contrast between Na(H2O)n and Na(NH3)n experiments is accounted for by the much smaller relaxation energy for Na(NH3)n, for which the structures and energetics are also elucidated.     

C4H5N-(NH3)n氢键团簇的多光子电力与从头计算

在３５５和５３２ｎｍ激光波长下用ＴＯＦ质谱仪研究了Ｃ４Ｈ５Ｎ－（ＮＨ３）ｎ系列氢键团簇体系的多光子电离,实验发现,两波长下除了得到一系列团簇离子Ｃ４Ｈ５Ｎ－（ＮＨ３）ｎ＾＋外,还观测到一系列质子化产物Ｃ４Ｈ５Ｎ－（ＮＨ３）ｎ－Ｈ＾＋,这些质子化产物来自于光电离过程中团簇内部的质子转移反应;Ｃ４Ｈ５Ｎ－（ＮＨ３）ｎ＾＋系列离子出现反常强度变化,即Ｃ４Ｈ５Ｎ－（ＮＨ３）２＾＋离子强度较Ｃ４Ｈ５Ｎ－（Ｎ     

吡啶团簇的飞秒光电离和从头计算研究

用飞秒激光电离飞行时间质谱研究了吡啶分子团簇在400 nm波长下的多光子光电离,实验观测到一系列的质子化和非质子化团簇离子.结果表明,质子转移也能发生在弱氢键结合的分子间.通过分析离子峰宽和离子信号强度随气源压力的变化,得到质子化团簇离子来源于大团簇离子的碎裂,而非质子化团簇离子是中性团簇直接电离的结果.从头计算结果表明,吡啶团簇是通过弱氢键C-H…N 结合在一起的,并且团簇离子离解倾向于生成质子化产物.     

Clusters of hydrated methane sulfonic acid CH3SO3H.(H2O)n (n = 1-5): a theoretical study

Ab initio and density functional methods have been used to examine the structures and energetics of the hydrated clusters of methane sulfonic acid (MSA), CH3SO3H.(H2O)n (n = 1-5). For small clusters with one or two water molecules, the most stable clusters have strong cyclic hydrogen bonds between the proton of OH group in MSA and the water molecules. With three or more water molecules, the proton transfer from MSA to water becomes possible, forming ion-pair structures between CH3SO3- and H3O+ moieties. For MSA.(H2O)3, the energy difference between the most stable ion pair and neutral structures are less than 1 kJ/mol, thus coexistence of neutral and ion-pair isomers are expected. For larger clusters with four and five water molecules, the ion-pair isomers are more stable (>10 kJ/mol) than the neutral ones; thus, proton transfer takes place. The ion-pair clusters can have direct hydrogen bond between CH3SO3- and H3O+ or indirect one through water molecule. For MSA.(H2O)5, the energy difference between ion pairs with direct and indirect hydrogen bonds are less than 1 kJ/mol; namely, the charge separation and acid ionization is energetically possible. The calculated IR spectra of stable isomers of MSA.(H2O)n clusters clearly demonstrate the significant red shift of OH stretching of MSA and hydrogen-bonded OH stretching of water molecules as the size of cluster increases.     

On the determination of monomer dissociation energies of small water clusters from photoionization experiments

Recently, monomer dissociation energies of neutral water clusters were estimated via a thermodynamic cycle that utilized the measured appearance energies of vacuum ultraviolet (VUV) photoionized water clusters and the previously reported dissociation energies of protonated water clusters. The thermodynamic cycle incorrectly assumed that the energy difference between the (H2O)n+ --> (H2O)n-1H+ + OH* asymptotes (the relaxation energy) was zero. We show that these relaxation energies are large and cannot be neglected in the analysis. Thus, the neutral water cluster monomer dissociation energies cannot be directly determined from the measured ionization potentials because they are themselves involved in the appropriate thermodynamic cycle.     

Microhydration of X2 gas (X = Cl, Br, and I): a theoretical study on X2.nH2O clusters (n = 1-8)

Structure and properties of hydrated clusters of halogen gas, X2.nH2O (X = Cl, Br, and I; n = 1-8) are presented following first principle based electronic structure theory, namely, BHHLYP density functional and second-order Moller-Plesset perturbation (MP2) methods. Several geometrical arrangements are considered as initial guess structures to look for the minimum energy equilibrium structures by applying the 6-311++G(d,p) set of the basis function. Results on X2-water clusters (X = Br and I) suggest that X2 exists as a charge separated ion pair, X+delta-X-delta in the hydrated clusters, X2.nH2O (n > or = 2). Though the optimized structures of Cl2.nH2O clusters look like X2.nH2O (X = Br and I) clusters, Cl2 does not exist as a charge separated ion pair in the presence of solvent water molecules. The calculated interaction energy between X2 and solvent water cluster increases from Cl2.nH2O to I2.nH2O clusters, suggesting solubility of gas-phase I2 in water to be a maximum among these three systems. Static and dynamic polarizabilities of hydrated X2 clusters, X2.nH2O, are calculated and observed to vary linearly with the size (n) of these water clusters with correlation coefficient >0.999. This suggests that the polarizability of the larger size hydrated clusters can be reliably predicted. Static and dynamic polarizabilities of these hydrated clusters grow exponentially with the frequency of an external applied field for a particular size (n) of hydrated cluster.     

Fragmentation characteristics of b(n) (n=2-15) ions from protonated peptides

The fragmentation reactions of protonated oligoalanines (trialanine, tetraalanine and pentaalanine) and the fragments present in the electrospray ionization (ESI) mass spectrum of polyalanine have been studied by collisionally activated dissociation (CAD) mass spectrometry (MS(2) and MS(3) experiments). The MS(n) experiments provided strong evidence that the m/z 71n+1 ion series in the ESI mass spectrum of polyalanine is a b(n) series. These ions are formed via the b(n) -y(m) pathway of amide bond cleavage, which results in the formation of a proton-bound complex of an oxazolone and a peptide/amino acid. Also, the MS(2) spectra of the b(n) series from polyalanine revealed that the chain length of b(n) ions influences significantly the dissociations taking place. For example, b(n) ions start losing H(2)O at n ≥5 and the losses of CO and CO+NH(3) decrease in intensity from b(2) to b(15). The elimination of H(2)O+NH(3) and the elimination of 61 mass (HN=C=O+H(2)O) commence with b(6); their abundances initially increase up to ~ b(8)-b(9) and then gradually decrease until b(15) (largest fragment studied). The tandem mass spectrometry experiments help to elucidate the dissociation mechanisms of the observed structures of biopolymer fragments.     

Guided ion-beam studies of the reactions of Co(n)+ (n=2-20) with O2: cobalt cluster-oxide and -dioxide bond energies

The kinetic-energy dependence for the reactions of Co(n)+ (n=2-20) with O2 is measured as a function of kinetic energy over a range of 0 to 10 eV in a guided ion-beam tandem mass spectrometer. A variety of Co(m)+, Co(m)O+, and Co(m)O2+ (m < or = n) product ions is observed, with the dioxide cluster ions dominating the products for all larger clusters. Reaction efficiencies of Co(n)+ cations with O2 are near unity for all but the dimer. Bond dissociation energies for both cobalt cluster oxides and dioxides are derived from threshold analysis of the energy dependence of the endothermic reactions using several different methods. These values show little dependence on cluster size for clusters larger than three atoms. The trends in this thermochemistry and the stabilities of oxygenated cobalt clusters are discussed. The bond energies of Co(n)+-O for larger clusters are found to be very close to the value for desorption of atomic oxygen from bulk-phase cobalt. Rate constants for O2 chemisorption on the cationic clusters are compared with results from previous work on cationic, anionic, and neutral cobalt clusters.     

Mid-infrared characterization of the NH4 +(H2O)n clusters in the neighborhood of the n=20 "magic" number

Vibrational predissociation spectra are reported for size-selected NH4+ (H2O)n clusters (n=5-22) in the 2500-3900 cm(-1) region. We concentrate on the sharp free OH stretching bands to deduce the local H-bonding configurations of water molecules on the cluster surface. As in the spectra of the protonated water clusters, the free OH bands in NH4+ (H2O)n evolve from a quartet at small sizes (n<7), to a doublet around n=9, and then to a single peak at the n=20 magic number cluster, before the doublet re-emerges at larger sizes. This spectral simplification at the magic number cluster mirrors that found earlier in the H+(H2O)n clusters. We characterize the likely structures at play for the n=19 and 20 clusters with electronic structure calculations. The most stable form of the n=20 cluster is predicted to have a surface-solvated NH4+ ion that lies considerably lower in energy than isomers with the NH4+ in the interior.     

IR+vacuum ultraviolet (118 nm) nonresonant ionization spectroscopy of methanol monomers and clusters: neutral cluster distribution and size-specific detection of the OH stretch vibrations

Small methanol clusters are formed by expanding a mixture of methanol vapor seeded in helium and are detected using vacuum UV (vuv) (118 nm) single-photon ionization/linear time-of-flight mass spectrometer (TOFMS). Protonated cluster ions, (CH3OH)(n-1)H+ (n=2-8), formed through intracluster ion-molecule reactions following ionization, essentially correlate to the neutral clusters, (CH3OH)n, in the present study using 118 nm light as the ionization source. Both experimental and Born-Haber calculational results clarify that not enough excess energy is released into protonated cluster ions to initiate further fragmentation in the time scale appropriate for linear TOFMS. Size-specific spectra for (CH3OH)n (n=4 to 8) clusters in the OH stretch fundamental region are recorded by IR+vuv (118 nm) nonresonant ion-dip spectroscopy through the detection chain of IR multiphoton predissociation and subsequent vuv single-photon ionization. The general structures and gross features of these cluster spectra are consistent with previous theoretical calculations. The lowest-energy peak contributed to each cluster spectrum is redshifted with increasing cluster size from n=4 to 8, and limits near approximately 3220 cm(-1) in the heptamer and octamer. Moreover, IR+vuv nonresonant ionization detected spectroscopy is employed to study the OH stretch first overtone of the methanol monomer. The rotational temperature of the clusters is estimated to be at least 50 K based on the simulation of the monomer rotational envelope under clustering conditions.     

Synthesis,crystal structure and magnetic properties of a series of polymeric lanthanoid–copper complexes [Ln2Cu3{O(CH2−CO2)2}6]·nH2O (Ln=La,Nd, n=9; Ln=Er,n=6)

The reaction of diglycolic acid, O(CH2CO2H)2, with Cu(NO3)2·2H2O and lanthanoid nitrate hydrate produces a series of novel Ln–Cu mixed metal complexes, [Ln2Cu3{O(CH2CO2)2}6]·nH2O (Ln=La, Nd, n=9; Ln=Er, n=6), which have been characterized by elemental analysis, i.r. spectroscopy, magnetic measurements and X-ray crystallography. The Ln3+ and Cu2+ ions are connected by the carboxylate groups of the ligands, resulting in the formation of a complicated network.     

Hydrogen bonds in 1,4-dioxane/ammonia binary clusters

With synchrotron radiation, we have studied the photoionization and dissociation of 1,4-dioxane/ammonia clusters in a supersonic expansion. The observed major product ions are the 1,4-dioxane cation M(+) and protonated cluster ions M(NH(3))(n)H(+) (where M=1,4-dioxane), and the intensities of the unprotonated cluster ions M(NH(3))(n) (+) are much lower. Fully optimized geometries and energies of the neutral cluster M(NH(3))(2) and related cluster ions have been obtained using the ab initio molecular orbital method and density functional theory. The potential energy surface of the excited state of M(NH(3))(2) (+) was also calculated. With these results, the mechanisms of different photoionization-dissociation channels have been suggested. The most probable channel is electron ejection from the highest occupied molecular orbital, followed by the dissociation into M(+) and (NH(3))(2). For another main channel, after removing an electron from the second highest occupied molecular orbital, the intracluster proton transfer process takes place to form the stable unprotonated cluster ion M(NH(3))H(+)-NH(2), which usually leads to the dissociated protonated cluster ion M(NH(3))H(+) and a radical NH(2).     

Electron impact ionization of water-doped superfluid helium nanodroplets: observation of He(H(2)O)(n)(+) clusters

Electron impact mass spectra have been recorded for helium nanodroplets containing water clusters. In addition to identification of both H(+)(H(2)O)(n) and (H(2)O)(n)(+) ions in the gas phase, additional peaks are observed which are assigned to He(H(2)O)(n)(+) clusters for up to n=27. No clusters are detected with more than one helium atom attached. The interpretation of these findings is that quenching of (H(2)O)(n)(+) by the surrounding helium can cool the cluster to the point where not only is fragmentation to H(+)(H(2)O)(m) (where m < or = n-1) avoided, but also, in some cases, a helium atom can remain attached to the cluster ion as it escapes into the gas phase. Ab initio calculations suggest that the first step after ionization is the rapid formation of distinct H(3)O(+) and OH units within the (H(2)O)(n)(+) cluster. To explain the formation and survival of He(H(2)O)(n)(+) clusters through to detection, the H(3)O(+) is assumed to be located at the surface of the cluster with a dangling O-H bond to which a single helium atom can attach via a charge-induced dipole interaction. This study suggests that, like H(+)(H(2)O)(n) ions, the preferential location for the positive charge in large (H(2)O)(n)(+) clusters is on the surface rather than as a solvated ion in the interior of the cluster.