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A Borodin

Publications and source records attributed to A Borodin.

10 recordsLinked to original sources
PubMed2006

Interaction of acetic acid with solid water.

The interaction of acetic acid (AA, CH(3)COOH), with solid water, deposited on metals, tungsten and gold, at 80 K, was investigated. We have prepared acid/water interfaces at 80 K, namely, acid layers on thin films of solid water and H(2)O adlayers on thin acid films; they were annealed between 80 and 200 K. Metastable impact electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy UPS(HeII) were utilized to obtain information on the electronic structure of the outermost surface from the study of the electron emission from the weakest bound MOs of the acids, and of the molecular water. Temperature-programmed desorption (TPD) provided information on the desorption kinetics, and Fourier-transformed infrared spectroscopy (FTIR) provided information on the identification of the adsorbed species as well as on the water and acid crystallization. The results are compatible with the finding of ref 1 (preceding paper), made on the basis of DFT calculations, that AA adsorbs on ice as cyclic dimers. Above 120 K, a rearrangement of the AA dimers is suggested by a sharpening of the spectral features in the IR spectra and by spectral changes in MIES and UPS; this is attributed to the glass transition in AA around 130 K. Above 150 K the spectra transform into those characteristic for polycrystalline polymer chains. This structure is stable up to about 180 K; desorption of water takes place from underneath the AA film, and practically all water has desorbed through the AA film before AA desorption starts. There is no indication of water-induced deprotonation of the acid molecules. For the interaction of H(2)O molecules adsorbed on amorphous AA films, the comparison of MIES with the DFT results of ref 1 shows that the initial phase of exposure does not lead to the formation of a top-adsorbed closed water film at 80 K. Rather, the H(2)O molecules become attached to or incorporated into the preexisting AA network by H bonding; no water network is formed in the initial stage of the water adsorption. Also under these conditions no deprotonation of the acid can be detected.

Journal Article↗
PubMed2005

The interaction of CO2 with sodium-promoted W(011).

The activation of CO2 by interaction with Na atoms on tungsten was studied in a joint experimental/theoretical effort combining MIES, UPS (HeII) and first principles calculations. Experimentally, both the adsorption of Na on tungsten, followed by CO2 exposure to the Na-modified surface at 80 K, and the adsorption of CO2 on tungsten, followed by Na exposure to the CO2 covered substrate, were studied. Below about 120 K CO2 physisorbs on pure W(011), and the distance between the three main spectral features is as for gas phase CO2 (E(B) = 8.4, 12.1, 14.1 eV). When offered to a Na monolayer (ML) deposited onto W, CO2 is converted into a chemisorbed species. The spectral pattern is different from physisorbed CO2, and the three spectral features are shifted towards lower binding energies (E(B) = 6.3, 10.7, 13.9 eV). The chemisorption continues until all available Na species are converted into Na+ species. Additional CO2 offered to the system becomes physisorbed on top of the chemisorbed species. When a CO2 monolayer, physisorbed on tungsten at 80 K, is exposed to Na, the interaction leads initially to a decrease of the surface work function and to a rigid, global shift of all CO2 induced features towards larger binding energies by about 2 eV. Only beyond a minimum Na coverage of about 0.5 ML, chemisorbed species can be detected. We conclude that, initially, transfer of the Na(3s) electron to the tungsten substrate takes place. Above 0.5 ML Na coverage, back donation of charge to CO2 takes place whereby the physisorbed carbon dioxide species become converted into chemisorbed ones. The experimental results are interpreted with the help of first principle calculations carried out on suitable slab models. The structures and surface binding mode of the chemisorbed CO2 species are described. The calculated density of states for the most stable situations is in qualitative agreement with experimental data.

Adsorption↗
PubMed2005

Interaction of CsF with multilayered water.

The interaction of CsF with multilayered water has been investigated with metastable impact electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy with HeI (UPS(HeI)). We have studied the emission from the ionization of H2O states 1b1, 3a1, and 1b2; of Cs5p and of F2p. We have prepared CsF-H2O interfaces, namely, CsF layers on thin films of multilayered water and vice versa; they were annealed between 80 and about 280 K. Up to about 100 K, a closed CsF layer can be deposited on H2O and vice versa; no interpenetration of the two components H2O and CsF could be observed. Above 110 K, CsF (H2O) layers deposited on thin H2O (CsF) films (stoichiometry CsF.1.5H2O) gradually transform into a mixed layer containing F, Cs, and H2O species. When annealing, H2O molecules can be detected up to 200 K from the mixed F-Cs-H2O layer (while for pure H2O desorption is essentially complete at 165 K); a water network is not formed under these conditions, and all H2O molecules are involved in bonding with Cs+ and F- ions. When CsF is deposited at 120 K on sufficiently thick water multilayers, full solvation of both F and Cs takes place, even for the species closest to the surface, as long as the stoichiometry remains CsF.(H2O)n with n > 3.

Journal Article↗
PubMed2005

Interaction of formic acid with solid water.

The interaction of formic acid (HCOOH) with solid water, deposited on tungsten at 80 K, was investigated. We have prepared and annealed formic acid (FA)/water interfaces (FA layers on thin films of solid water and H(2)O adlayers on thin FA films). Metastable impact electron spectroscopy and ultraviolet photoemission spectroscopy (He I and II) were utilized to study the electron emission from the 10a' to 6a' molecular orbitals (MOs) of FA, and the 1b(1), 3a(1), and 1b(2) MOs of H(2)O. These spectra were compared with results of density-functional theory calculations on FA-H(2)O complexes reported in Ref. 14 [A. Allouche, J. Chem. Phys. 122, 234703(2005), (preceding paper)]. Temperature programmed desorption was applied for information on the desorption kinetics. Initially, FA is adsorbed on top of the water film. The FA spectra are distorted with respect to those from FA monomers; it is concluded that a strong interaction exists between the adsorbates. Even though partial solvation of FA species takes place during annealing, FA remains in the top layer up to the desorption of the water film. When H(2)O molecules are offered to FA films at 80 K, no water network is formed during the initial stage of water exposure; H(2)O molecules interact individually via H bonds with the formic acid network. Experiment and theory agree that no water-induced deprotonation of the formic acid molecules takes place.

Journal Article↗
PubMed2004

Interaction of NaCl with solid water.

The interaction of NaCl with solid water, deposited on tungsten at 80 K, was investigated with metastable impact electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy (UPS) (He I). We have studied the ionization of Cl(3p) and the 1b(1), 3a(1), and 1b(2) bands of molecular water. The results are supplemented by first-principles density functional theory (DFT) calculations of the electronic structure of solvated Cl(-) ions. We have prepared NaCl/water interfaces at 80 K, NaCl layers on thin films of solid water, and H(2)O ad-layers on thin NaCl films; they were annealed between 80 and 300 K. At 80 K, closed layers of NaCl on H(2)O, and vice versa, are obtained; no interpenetration of the two components H(2)O and NaCl was observed. However, ionic dissociation of NaCl takes place when H(2)O and NaCl are in direct contact. Above 115 K solvation of the ionic species Cl(-) becomes significant. Our results are compatible with a transition of Cl(-) species from an interface site (Cl in direct contact with the NaCl lattice) to an energetically favored configuration, where Cl species are solvated. The DFT calculations show that Cl(-) species, surrounded by their solvation shell, are nevertheless by some extent accessed by MIES because the Cl(3p)-charge cloud extends through the solvation shell. Water desorption is noticeable around 145 K, but is not complete before 170 K, about 15 K higher than for pure solid water. Above 150 K the NaCl-induced modification of the water network gives rise to gas phase like structures in the water spectra. In particular, the 3a(1) emission turns into a well-defined peak. This suggests that under these conditions water molecules interact mainly with Cl(-) rather than among themselves. Above 170 K only Cl is detected on the surface and desorbs around 450 K.

Journal Article↗
PubMed2004

Electron delocalization by polar molecules: interaction of Na atoms with solid ammonia films studied with MIES and density functional theory.

The interaction of Na and NH(3) on tungsten was studied with metastable impact electron spectroscopy under UHV conditions. NH(3)(Na) films were grown at 90(+/-10) K on tungsten substrates and exposed to Na(NH(3)). No Na-induced reaction involving NH(3) takes place. At small Na exposures a Na-induced shift of the NH(3) spectral features is seen, in parallel with a decrease of the surface work function. At larger exposures three 3sNa-related spectral structures are seen, two of them at energetic positions different from that found for Na on metals or semiconductors. The main additional peak is attributed to delocalized Na species. A small additional feature is attributed to simultaneous ionization and excitation of partially ammoniated Na(2) species. The results are compared with density functional theory calculations which suggest that the 3sNa emission at small exposures appears to originate mainly from delocalized 3sNa electrons; they are located far from the Na species and become stabilized by solvent molecules. When depositing NH(3) molecules onto Na films, metalliclike Na patches and delocalized Na species coexist. The delocalization of 3sNa is seen up to T=130 K where the NH(3) species desorb.

Journal Article↗
PubMed2004

Electron solvation by polar molecules: the interaction of Na atoms with solid methanol films studied with MIES and density functional theory calculations.

The interaction of Na atoms with CH(3)OH films was studied with metastable impact electron spectroscopy (MIES) under UHV conditions. The films were grown at 90(+/-10) K on tungsten substrates and exposed to Na. Na-induced formation of methoxy (CH(3)O) species takes place, and Na atoms become ionized. At small Na exposures the outermost solvent layer remains largely intact as concluded from the absence of MIES signals caused by the reaction products. However, emission from CH(3)O, located at the film surface, occurs at larger exposures. In the same exposure range also Na species can be detected at the surface. The spectral feature from 3s Na ionization occurs at an energetic position different from that found for metals or semiconductors. The results are compared with density functional theory calculations [see Y. Ferro, A. Allouche, and V. Kempter, J. Chem. Phys. 120, 8683 (2004), preceding paper]. Experiment and theory agree in the energetic positions of the main spectral features from the methanol and sodium ionization. The calculations suggest that the 3s Na emission observed experimentally originates from solvated 3s electrons which are located far from the Na core and become stabilized by solvent molecules. The simultaneous emergence of emission from CH(3)O and from solvated 3s electrons suggests that the delocalization and, consequently, the solvation play an important role in the Na-induced formation of CH(3)O from CH(3)OH.

Journal Article↗
PubMed2004

The interface between benzenes (C6H6;C6H5Cl;2-C6H4OHCl) and amorphous solid water studied with metastable impact electron spectroscopy and ultraviolet photoelectron spectroscopy (HeI and II).

Interfaces between films of benzenes (C(6)H(6);C(6)H(5)Cl;2-C(6)H(4)OHCl) and solid H(2)O on tungsten substrates were studied between 80 and 200 K with metastable impact electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy [UPS(HeI and II)]. The following cases were studied in detail: (i) Adsorption of the benzenes on solid water in order to simulate their interaction with ice particles, and (ii) deposition of water on benzene films in order to simulate the process of water precipitation. In all cases the prepared interfacial layers were annealed up to 200 K under in situ control of MIES and UPS. The different behavior of the interfaces for the three studied cases is traced back to the different mobilities of the molecules with respect to that of water. The interaction between H(2)O and the benzenes at the interfaces is discussed on the basis of a qualitative profile for the free energy of that component of the interface which has the larger mobility. Possible implications of the present results for atmospheric physics are briefly mentioned.

Journal Article↗
PubMed1995

An arrayed library enriched in hncDNA corresponding to transcribed sequences of human chromosome 19: preparation and analysis.

A simple technique for preparation of libraries of the human chromosome specific transcribed sequences is developed. It uses hnRNA from human-rodent hybrid cell lines containing particular human chromosomes or their fragments and includes three stages: (i) reverse transcription of the hnRNA with Alu-specific primers directing the transcription beyond the Alu-repeats to flanking non-repetitive sequences of the chromosome; (ii) nested primer PCR strategy with specifically designed primers; (iii) direct selective cloning of the second-stage nested primer PCR products. An arrayed hncDNA library was prepared from a hybrid cell line containing chromosome 19 and fragments of 22 and X chromosomes. The library contains around 98% of human-specific transcribed sequences. Sequences of 52 human-specific, according to PCR analysis, clones differed from each other and had no close analogs in the EMBL Data Bank. Of 17 clones assigned to certain human chromosomes, 9 belonged to chromosome 19, 5 to chromosome 22 and 3 to chromosome X. Some of the human specific clones contained repetitive elements scattered over different human chromosomes. Clones from hncDNA libraries are useful as STSs/ESTs, as probes for detecting full-size genes in genomic libraries, for RFLP analysis and for identification of chromosome specific cDNAs.

Animals↗