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1.
J Am Soc Mass Spectrom ; 16(5): 733-42, 2005 May.
Article in English | MEDLINE | ID: mdl-15862774

ABSTRACT

We investigate the mechanism of the nonlinear secondary ion yield enhancement using Au(n)+ (n = 1, 2, 3, 5, 7) primary ions bombarding thin films of Irganox 1010, DL-phenylalanine and polystyrene on Si, Al, and Ag substrates. The largest differences in secondary ion yields are found using Au+, Au2+, and Au3+ primary ion beams. A smaller increase in secondary ion yield is observed using Au5+ and Au7+ primary ions. The yield enhancement is found to be larger on Si than on Al, while the ion yield is smaller using an Au+ beam on Si than on Al. Using Au(n)+ ion structures obtained from Density Functional Theory, we demonstrate that the secondary yield enhancement is not simply due to an increase in energy per area deposited into the surface (energy deposition density). Instead, based on simple mechanical arguments and molecular dynamics results from Medvedeva et al, we suggest a mechanism for nonlinear secondary ion yield enhancement wherein the action of multiple concerted Au impacts leads to efficient energy transfer to substrate atoms in the near surface region and an increase in the number of secondary ions ejected from the surface. Such concerted impacts involve one, two, or three Au atoms, which explains well the large nonlinear yield enhancements observed going from Au+ to Au2+ to Au3+ primary ions. This model is also able to explain the observed substrate effect. For an Au+ ion passing through the more open Si surface, it contacts fewer substrate atoms than in the more dense Al surface. Less energy is deposited in the Si surface region by the Au+ primary ion and the secondary ion yield will be lower for adsorbates on Si than on Al. In the case of Au(n)+ the greater density of Al leads to earlier break-up of the primary ion and a consequent reduction in energy transfer to the near-surface region when compared with Si. This results in higher secondary ion yields and yield enhancements on silicon than aluminum substrates.


Subject(s)
Aluminum/analysis , Gold/analysis , Gold/chemistry , Membranes, Artificial , Silicon/analysis , Spectrometry, Mass, Electrospray Ionization/methods , Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization/methods , Aluminum/chemistry , Computer Simulation , Ions , Models, Chemical , Silicon/chemistry
2.
J Chem Phys ; 122(9): 094310, 2005 Mar 01.
Article in English | MEDLINE | ID: mdl-15836131

ABSTRACT

We performed density functional theory calculations at the PW91PW91/LANL2DZ, PW91PW91/Stuttgart 1997, PW91PW91/CRENBL, B3LYP/LANL2DZ, and SVWN5/LANL2DZ levels of theory to attain the minimum-energy structures of neutral and cationic gold clusters of up to nine gold atoms. We locate the 2D-to-3D (two-dimensional to three-dimensional) transition in cationic clusters as occurring between Au(8) (+) and Au(9) (+). We also demonstrate that we can correlate the 2D-to-3D transition in cationic clusters with a linear extrapolation of the energy differences of the lowest-lying 2D and 3D structures of cluster sizes below the transition. We then use the same approach to predict that the 2D-to-3D transition occurs in neutral clusters at Au(11); this is confirmed by locating 3D Au(11) structures that are lower in energy than the best 2D structures reported to date. We examine the effects of choice of basis sets and exchange-correlation functionals on the relative stabilities and other properties of the calculated structures. Finally we find that there is good agreement between calculated and experimental data for clusters with up to six constituent atoms. For clusters with more than seven atoms, there are significant differences observed between the calculated and experimental properties using SVWN5/LANL2DZ, but there is still good agreement for the other levels of theory used.

3.
J Phys Chem B ; 109(22): 11263-72, 2005 Jun 09.
Article in English | MEDLINE | ID: mdl-16852375

ABSTRACT

In situ time-of-flight secondary ion mass spectrometry, infrared spectroscopy, and X-ray photoelectron spectroscopy measurements have been used to characterize the interfacial chemistry that occurs upon physical vapor deposition of Ti and Ca atoms onto a -OCH(3) terminated alkanethiolate self-assembled monolayer (SAM) on Au{111}. While the final result for both metals is near-exhaustive degradation of the methoxy terminal group and partial degradation of the alkyl chains to inorganic products such as carbides, hydrides, and oxides, the reaction mechanisms differ significantly. Titanium reacts in parallel with the -OCH(3) and -CH(2)- units, extensively degrading the latter until a metallic overlayer forms preventing further degradation. At this point, there is a cessation of the Ti-SAM reactions. In contrast, Ca is initially consumed by the -OCH(3) terminal group via a reaction mechanism involving two -OCH(3) groups; subsequent depositions lead to alkyl chain degradation, but at a rate slower than that for Ti deposition. These results demonstrate the subtle differences in chemistry that can arise in the vapor deposition of reactive metals, and have important implications for the behavior of electrical interfaces in organic and molecular devices made with Ti or Ca top contacts.

4.
J Appl Clin Med Phys ; 3(4): 263-72, 2002.
Article in English | MEDLINE | ID: mdl-12383046

ABSTRACT

The loading of needles for loose seed implantation of the prostate gland results requires a significant amount of effort and some radiation exposure to members of the medical staff. This study was performed to quantify the time spent and exposure levels associated with implant preparation, as well as to investigate any improvement in the time or exposure burden due to the introduction of a new loading device. The movements and radiation exposures for two single, highly experienced dosimetrists were monitored for ten conventionally loaded iodine implant cases. These same cases were reloaded with dummy sources using the sleeved system to determine time savings, if any. Two of these ten cases were then loaded with live sources using the sleeved system to determine relative exposure to the loading staff between the two methods. The results were then analyzed to generate per-seed and per-needle loading time and exposure burdens. Formulas are presented that may be used to determine the average time to load implants and the resultant staff exposure, both with the conventional technique and with the sleeved method. On the average, it takes an experienced loader 48 min to prepare an implant for the operating room, receiving a hand dose of about 10 mrem and a whole body dose of about 1 mrem. The sleeved system reduced these values by at least half. The time and exposure burden associated with the preparation of iodine loose seed implants has been characterized. The use of the sleeved needles resulted in significant time and exposure reductions for the medical staff.


Subject(s)
Brachytherapy/methods , Prostate/radiation effects , Brachytherapy/economics , Brachytherapy/instrumentation , Humans , Iodine Radioisotopes/adverse effects , Iodine Radioisotopes/therapeutic use , Male , Mathematical Computing , Medical Staff, Hospital , Occupational Exposure/classification , Radiotherapy Planning, Computer-Assisted/methods , Time Factors
5.
J Pastoral Care ; 47(2): 149-56, 1993.
Article in English | MEDLINE | ID: mdl-10127080

ABSTRACT

Describes some characteristics of certain learning disabilities in children and how a chaplain can provide effective pastoral care to the dysfunctional child. Notes through clinical vignettes how a chaplain can communicate God's love and faithfulness to children who suffer from attention deficits and hyperactivity disorders.


Subject(s)
Chaplaincy Service, Hospital , Child, Hospitalized/psychology , Hospitals, Psychiatric , Pastoral Care/methods , Attention Deficit Disorder with Hyperactivity/psychology , Attention Deficit Disorder with Hyperactivity/therapy , Child , Clergy , Female , Florida , Humans , Learning Disabilities/psychology , Learning Disabilities/therapy , Male
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