Properties of Phagraphene via Hydrogenation and Fluorination

Properties of Phagraphene via Hydrogenation and Fluorination Modulation of electronic and mechanical properties of phagraphene via hydrogenation and fluorination Donghai Wu ab, Shuaiwei Wang ab, Jinyun Yuanab* Baocheng Yang ab, Houyang Chenc* a Institute of Nanostructured Functional Materials, Huanghe Science and Technology College, Zhengzhou, Henan 450006, China b Henan provincial key laboratory of nanocomposite and application, Zhengzhou, Henan 450006, China c Department of Chemical and Biological Engineering, State University of New York at Buffalo, Buffalo, New York 14260-4200, USA ________________ Abstract: Recently, a new carbon sheet, phagraphene, was proposed by theoretical calculations [Nano Lett. 2015, 15, 6182]. In this paper, the hydrogenated and fluorinated phagraphene (denoted as H-PHA and F-PHA) sheets have been systematically studied using first-principles calculations. The results of formation energy, ab initio molecular dynamics, phonon dispersion and elastic constants confirm that the modified phagraphene sheets are thermodynamically and dynamically as well as mechanically stable. We find that hydrogenation or fluorination is an effective way to modulate the bandgap, and we also find that adsorption-induced semimetal-semiconductor transition and adsorption-induced semimetal-insulator transition occur. Configuration-dependent bandgap for partially H-PHA and configuration-independent bandgap for fully H-PHA are determined. Adsorption-ratio-dependent bandgaps of H-PHA and F-PHA are also identified. Calculated bandgaps from HSE06 and PBE functionals of fully H-PHA ar e larger than those of F-PHA, and they are comparable to thehydrogenated/fluorinated penta-graphene while they are larger than their corresponding graphene. Dependence of bandgaps of fully H-PHA and F-PHA on the tensile strain is investigated, and our calculations show that an insulator-semiconductor transition occurs upon increasing the tensile strain. Our results also determined that the mechanical properties are controllable by using hydrogenation and fluorination. The calculations of Youngs modulus and Poissons ratio reveal the functionalized phagraphene sheets possess suitable stiffness and resistance to volume deformation, and both are smaller than the pristine phagraphene. 1. Introduction Two-dimensional (2D) carbon-based materials have been attracting great attention due to their fascinating mechanical, thermal, electronic, optical and magnetic properties.1-11 In particular, graphene is the most representative example. Since synthetized by Novoselov et al.6 in 2004, graphene has been extensively studied for its robust stability,12 high crystal quality,13 captivating mechanical and electronic as well as thermal properties.14-18 The covalently bonded honeycomb lattice with perfect hexagonal symmetry of graphene plays a crucial role in forming Dirac cones,19 which gives graphene massless fermions, resulting in the anomalous quantum Hall effects,20 ultrahigh carrier mobility21 and other properties.22, 23 Recently, a new carbon sheet, phagraphene,19 composed of rings containing five, six, and seven carbon atoms, was proposed by theoretical calculations. It can be considered as a defective graphene.24 This planar carbon allotrope is slightly more unstable than pristine graphene while energetically more favorable than other carbon allotropes.19 The notable stability benefits from its sp2-hybridization and dense atomic packing structure.25 Zhang et al.19 have proven that the electronic structure of phagraphene has direction-dependent Dirac cones, which are robust against external strain with tunable Fermi velocities. This unique performance makes the phagraphene an advanced material for numerous applications in photoelectric technology. However, like graphene, the phagraphene suffers a major drawback of zero bandgap and rather robust gapless state, limiting its potential applications. In order to overcome this disadvantage, we use hydrogenation and fluorination to modulate its bandgap in this paper. Thanks to the surface unsaturated C-C dangling bond,26 the chemical modification by adsorbing non-carbon atoms on the surface is an effective way to create a bandgap and tune the electronic, magnetic and mechanical properties of graphene.14, 24, 26-32 Hydrogenation is not only the simplest and manageable adsorption but also the generating hydrides are promising hydrogen storage materials in energy field.33, 34 The fluorine atoms with ultrahigh electronegativity are adsorbed on the graphene surface forming fluorinated graphene, which have been investigated experimentally and theoretically.14, 35, 36 After adsorbing such atoms, the forming C-H and C-F bonds could give rise to the carbon atoms transforming their hybridizati on state from sp2 to sp3, 33 correspondingly, the structural and electronic properties would undergo dramatic alterations. In this work, by employing first-principles calculations, the effect of hydrogenation and fluorination on the bandgap opening of phagraphene sheet is examined. After hydrogenation or fluorination, the bandgap of phagraphene could be opened sizably, changing its electro-conductivity from Dirac semimetal to semiconductor or from Dirac semimetal to insulator. The structural stability and mechanical properties of the modified phagraphene sheet are also investigated. 2. Computational details All the first-principles calculations and abinitio molecular dynamics (AIMD) were carried out by density functional theory (DFT) with the projector augmented wave (PAW) method and performed by the Vienna abinitio simulation package (VASP)37 . The 2D periodic boundary condition was adopted and a vacuum space of 20 Ã… along the perpendicular direction of the phagraphene sheet was included in order to avoid the interactions between adjacent layers. The generalized gradient approximation (GGA) of Perdew, Burke, and Ernzerhof (PBE)38 was applied as the exchange-correlation functional in most of the calculations. Meanwhile, to accurately calculate the band structures, the hybrid Heyd-Scuseria-Ernzerhof (HSE06)39 was introduced. The Brillouin zone (BZ) was sampled using 2à Ã¢â€š ¬ ÃÆ'- 0.01 Ã…Ã ¢Ã‹â€ Ã¢â‚¬â„¢1 Monkhorst-Pack40 k-point mesh density, and the plane-wave basis set with cutoff energy of 600 eV was adopted. The total energy difference of 10à ¢Ã‹â€ Ã¢â‚¬â„¢5 eV and forc e tolerance of 10à ¢Ã‹â€ Ã¢â‚¬â„¢2 eVà ¢Ã¢â€š ¬Ã‚ ¢Ãƒâ€¦Ãƒ ¢Ã‹â€ Ã¢â‚¬â„¢1 were used for the convergence criteria of geometric optimization and self-consistent field. The phonon properties were calculated by the Phonopy package41 with force constants obtained by the finite displacement method.42 3. Results and discussion 3.1 Structural properties Figure 1 displays the structure of phagraphene19 together with its hydride and fluoride. The hydrogenated or fluorinated phagraphene (denoted as H-PHA or F-PHA) sheet is obtained by adsorbing hydrogen or fluorine atoms on both sides of the plane. For fully H-PHA and F-PHA, the ratio of C : H/F is 1 : 1. After optimization, the structures of both fully H-PHA (Figure 1c) and fully F-PHA (Figure 1d) are greatly distorted compared to pristine phagraphene (Figure 1a), resulting in low symmetry with a space group of P21/m (No. 11). The 5-6-7 carbon rings no longer remain in the same plane and become crumpled. The buckling height hb (i.e. the height between the bottom and top carbon layers) of fully H-PHA (0.856 Ã…, see Table 1) is larger than that of F-PHA (0.704 Ã…), and they are much larger than those of hydrogenated/fluorinated penta-graphene (0.42/0.40 Ã…) and graphene (0.46/0.49 Ã…).12 The calculated C-C bond distances of pristine phagraphene in Table 1 are in agreement wi th previous calculations,19 indicating the computational method is valid. All the C-C bond distances in fully H-PHA and fully F-PHA are enlarged compared to the pristine phagraphene, and are close to that of 1.546 Ã… in diamond43 while larger than that of 1.42 Ã… in graphene.1 These facts indicate the C-C bonds of phagraphene transform from the sp2-hybridization double bond to the sp3 single bond by hydrogenation or fluorination. The C-C bonds of fully F-PHA are longer than those of fully H-PHA, which can be explained by the depopulation of bonding orbitals between carbon atoms.27 The depopulation of these bonding orbitals stems from the electron transfer between carbon and hydrogen/fluorine atoms. The C-C bonds (C4-C4 in Figure 1) connecting the adjacent 5- and 7-carbon rings are enlarged to a greater extent than others, which is because of the repulsive interactions and steric effects between the adjacent two H/F atoms in the same side of phagraphene. The C-H and C-F bond di stances are approximately 1.11 and 1.38 Ã… (Table S1), approaching to the typical hydrocarbon and fluorocarbons compounds.44 Similar structure distortions and C-C bond elongation are found in hydrogenated/fluorinated penta-graphene and graphene.12, 26, 44 3.2 Stability analysis To investigate the stability of H-PHA and F-PHA, the binding energy Eb and formation energyEf are calculated (definitions of Eb and Ef are given at Section S1 of Supporting Information). The values of Eb are -2.540 and -2.977 eV/atom for fully H-PHA and fully F-PHA (see Table 1), respectively, implying strong interactions between C and H/F. A possible explanation of the strong attractive interactions between C atoms (of phagraphene) and H/F atoms is that, by adsorbing H/F atoms, the C-H/C-F bonds are formed, and the C-C bonds of phagraphene elongate greatly, which could partially release the stress imposed by the 5-6-7 carbon rings.12 Another important factor for synthesis is the formation energy, which applies to measure the stability against molecular desorption from the surface.44 The negative Ef (-0.276 eV/atom for fully H-PHA and -1.615 eV/atom for fully F-PHA) means that the surface modification is exothermic process and the H-PHA (or F-PHA) has lower energy than that of pristi ne phagraphene and H2 (or F2) molecules. The Eb and Ef of hydride are larger than those of fluoride, which are in accordance with similar systems of hydrogenated/fluorinated graphene (-2.48 eV > -2.86 eV)27 and penta-graphene (-3.65 eV > -4.22 eV).12 It is noticed that the Eb of fully H-PHA and fully F-PHA are close, whereas the Ef of fully H-PHA and fully F-PHA have huge difference. This is because of large difference in the dissociation energy of H2 and F2 molecules.27 The thermal stability is also important for H-PHA and F-PHA and is evaluated using the AIMD simulations with a 2 ÃÆ'- 2 ÃÆ'- 1 supercell and a time step of 1 fs for 5000 steps at room temperature (300 K) and 1000 K. Temperature (T) and total energy (Et) as functions of simulation time are plotted in Figures 2 and S1. T and Et converge to constants and the fully H-PHA and F-PHA keep their integrated structures during the AIMD simulations at the setting temperature. These facts demonstrate that hydrogenated or fluorinated phagraphene not only possesses robust thermal stability at room temperature, but also is resistant to high temperature such as 1000 K. In order to examine the dynamic stability, the phonon dispersion curves along the high symmetry points in the BZ and the corresponding phonon density of states (PDOS) are calculated  (Figure 3). No imaginary frequencies are found for both fully H-PHA and fully F-PHA, demonstrating that they are dynamically stable. There are three obvious acoustic modes in the bottom of the phonon spectra for the two structures, and the double degenerates arise along the XZ path of the BZ. These features are similar to the pristine phagraphene,19 graphene45 and its derivatives.12 From the PDOS, one can see that the H-PHA has a tremendous phonon gap of approximately 40 THz, while it is small for F-PHA (about 3 THz). The vibration frequency is inversely proportional to the effective atomic mass,12 thus the larger phonon gap of H-PHA than F-PHA may be attributed to the much lighter atomic mass of hydrogen than fluorine atom. Meanwhile, the narrow high frequency zone around 87 THz in Figure 3a is c orresponding to the C-H bond vibration modes of H-PHA, in accordance with the case of hydrocarbon.46 These C-H stretching modes are infrared active and useful in characterizing this compound.44 The low frequency range from 5 to 10 THz in Figure 3b mainly consists of the phonon modes of C-F bonds. The middle frequency range is dominated by the motion of C atoms. The C=C double bonds were broken by hydrogenation/fluorination, resulting in the disappearance of C-C vibration modes in the region of 40-50 THz for pristine phagraphene.19 3.3 Electronic structures In order to explore the electronic properties and bonding features, the band structures and density of states (DOS) of partially and fully hydrogenated/fluorinated phagraphene are calculated using both PBE and HSE06 functionals. As an example for partially H-PHA, 60% hydrogenation of phagraphene is chosen and four stable configurations (see Figure S2) are designed. The band structures of these configurations are shown in Figures 4 and S3. One can see that the band structures disperse greatly to single band, leading to the sharp peak appearing in the DOS at the EF. Meanwhile, a sub-bandgap located below or above the primary bandgap was observed. From calculations with PBE functional (Figure S3), the bandgaps of the four configurations vary from 2.65 eV (Figure S3a) to 1.72 eV (Figure S3b) to 0.93 eV (Figure S3c) to 0 (Figure S3d). The PBE functional usually underestimates the bandgap of materials.12 To obtain a more accurate Egap, the hybrid functional HSE06 is adopted. The calculated bandgaps with HSE functional in Figure 4 are 3.70 eV, 2.46 eV, 1.56 eV and 0.54 eV for the four configurations. Thus, one can conclude that the bandgap of partially hydrogenated phagraphene depends on configuration and adsorptio n-induced semimetal-semiconductor transition occurs. Such a functionalized 2D material with a proper bandgap has promising applications in optoelectronics and microelectronics.29, 47 The band structures and DOS of fully H-PHA and fully F-PHA are shown in Figures 5 and S4. From calculations with PBE functional (Figure S4), fully H-PHA and F-PHA have direct bandgaps of 4.29 eV and 3.23 eV, respectively. To examine the influence of configuration on the electronic properties, another four configurations of fully hydrogenated phagraphene (see Figure S5) are taken into account. The calculated band structures of the five configurations (Figures S4a and S6) are almost the same and the bandgaps are approximately 4.29 eV, indicating that the Egap of fully hydrogenated phagraphene is independent of the configuration. Similar behavior was found for fully hydrogenated graphene.27 We also calculated the band structures and DOS with HSE06 functional (Figure 5), and obtained that Egap for fully H-PHA and fully F-PHA are 5.37 and 4.98 eV, respectively. These values are comparable to the Egap of hydrogenated/fluorinated penta-graphene (5.35 eV and 4.78 eV) while they are larger th an those of corresponding graphene (4.97 eV and 4.74 eV).12 Obviously, the Egap of F-PHA is smaller than that of H-PHA. Similar results are found in cases of hydrogenated/fluorinated graphene26, 27 and penta-graphene.12Compared to the pristine phagraphene with zero bandgap, the surface modification via hydrogenation or fluorination can effectively tune its electronic structure from semimetal to insulator. Analysis of the partial DOS (Figure 5) reveals that, for H-PHA, the electronic states near the Fermi level (EF) are primarily originated from the C atoms, while they are dominated by both C and F atoms for F-PHA. Additional, from Figures 4 and 5, one can conclude that the bandgaps of H-PHA and F-PHA depend on the adsorption ratio of H and F atoms. We also examine the effect of strain on the band structures. The obtained stress-strain curves of fully H-PHA and F-PHA under biaxial loading (Figure S7) show that their fracture strains are 0.17 and 0.13, respectively. By changing the biaxial tensile strain, the bandgaps of fully H-PHA and F-PHA remain the direct gaps (Figures S8 and S9). Furthermore, upon increasing the biaxial tensile strain, the bandgap of fully H-PHA increases first and then decreases (Figure 6a), whereas the bandgap of fully F-PHA decreases monotonically (Figure 6b). These behaviors indicate that bandgaps depend on the strain. Strain-dependent bandgaps of other 2D materials were also determined previously.48-52 More interestingly, our calculations show that the bandgap of H-PHA reduces from 5.62 eV (ÃŽÂ µ = 0.10) to 4.42 eV (ÃŽÂ µ = 0.17) and the bandgap of F-PHA decreases from 4.98 eV (ÃŽÂ µ = 0) to 3.01 eV (ÃŽÂ µ = 0.13), indicating that an insulator-semiconductor transition occurs with the tensil e strain changes. To visually describe the electronic structure of fully H-PHA and F-PHA, we calculate the charge density. As shown in Figure 7, the charges are redistributed after hydrogenation or fluorination. Compared to the charge densities of C=C bonds in pristine phagraphene (see Figure S10), the charge densities of C-C bonds in H-PHA and F-PHA are reduced. For H-PHA, the shared charges donated by hydrogen are mainly located between the carbon and hydrogen atoms. For F-PHA, a large number of charges are focused on the fluorine atoms. This difference is a consequence of the different electronegativity of hydrogen and fluorine. For a selected element, its attraction of electrons becomes stronger with higher electronegativity.53, 54 The electronegativity increases gradually from hydrogen to carbon to fluorine.53 Thus the charge transfer is from hydrogen to carbon atoms in H-PHA while it is from carbon to fluorine atoms in F-PHA, which is consistent with other hydrocarbons and fluorocarbons.12, 55-5 7 Moreover, the charge density between H and C is lower than that between F and C, implying the weaker C-H interaction than C-F. The Mulliken population analysis58 shows that the transfer charge amounts are approximately 0.22 and 0.33 electrons for H-PHA and F-PHA, respectively, manifesting the weaker bond strength of C-H than that of C-F. 3.4 Mechanical properties Since the ultrathin 2D phagraphene as well as its derivatives is susceptible to external influences, including mechanical deformation,24 it is necessary to develop an in-depth understanding of their mechanical properties for practical application. The elastic constants are calculated (definitions are given at Section S2 of Supporting Information) and the obtained results are tabulated in Table 2, together with the existing reference data24 for comparison. All the elastic constants of fully H-PHA and fully F-PHA satisfy the mechanical stability criteria of C11C22 à ¢Ã‹â€ Ã¢â‚¬â„¢ C122 > 0 and C66 > 0 for 2D sheets,3, 59 indicating that they are mechanically stable. The in-plane Youngs modulus (E) and Poissons ratio (ÃŽÂ ½) can be derived from the elastic constants using the formulas of E = (C112 à ¢Ã‹â€ Ã¢â‚¬â„¢ C122) / C11 and ÃŽÂ ½ = C12 / C11.24 The E of fully H-PHA and F-PHA are 151.3 and 176.3 N/m (see Table 2), respectively, which are consistent with the results from the stress-strain curves (149.2 and 178.5 N/m for fully H-PHA and F-PHA, respectively). The Poissons ratio ÃŽÂ ½ of fully H-PHA and F-PHA are 0.078 and 0.152, respectively. Because the larger E implies the stronger stiffness and the larger Poissons ratio signifies the stronger incompressibility,24 the F-PHA has better stiffness and resistance to volume compression than the H-PHA, which may ascribe to the stronger C-F bonds than C-H bonds. Compared to pristine phagraphene, the E and ÃŽÂ ½ of H-PHA and F-PHA are significantly reduced. Such reduction may be related to their different charge density distribution and bond nature.12, 24 4. Conclusions In summary, we systematically study the structure, stability, electronic and mechanical properties of hydrogenated and fluorinated phagraphene sheets. Our results show that H-PHA and F-PHA are thermodynamically and dynamically as well as mechanically stable. The binding energy and formation energy of fully F-PHA are smaller than those of fully H-PHA, implying the stronger stability of F-PHA than H-PHA. After hydrogenation or fluorination, the bandgap of phagraphene is opened properly, resulting in an adsorption-induced semimetal-semiconductor transition or adsorption-induced semimetal-insulator transition. Strain-induced insulator-semiconductor transition is also identified. Our band structures demonstrate that bandgap of fully H-PHA is insensitive to the configuration whereas the bandgap of partially H-PHA is sensitive to the configuration. Adsorption-ratio-dependent of H-PHA and F-PHA is also determined. The obtained bandgaps from both PBE and HSE06 functionals of fully F-PHA are s maller than fully H-PHA. The charges are transferred from hydrogen to carbon atoms in the fully H-PHA while it is from carbon to fluorine atoms in the fully F-PHA. The positive Poissons ratios of fully H-PHA and F-PHA manifest that they can well resist the volume deformation.Both the Youngs moduli and Poissons ratios of the two phagraphene derivatives are significantly smaller than the pristine phagraphene. This investigation suggests that hydrogenation or fluorination is an effective strategy to modulate the electronic and mechanical properties of phagraphene for its possible applications in nanoelectronics. Acknowledgements The authors acknowledge the National Natural Science Foundation of China (21401064, 21206049 and 51472102), the Natural Science Foundation of the Education Department of Henan Province (15A150060), the National Natural Science and Henan Province United Foundation of China (U1204601), Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase), and Leading Talents for Zhengzhou Science and Technology Bureau (Grant No. 131PLJRC649) for supports. We thank the National Supercomputer Center in Guangzhou and the High performance Computing Center of Huanghe Science and Technology College for the computer time provided. References 1.A. H. Castro Neto, F. Guinea, N. M. R. Peres, K. S. Novoselov and A. K. Geim, Rev. Mod. Phys., 2009, 81, 109-162. 2.D. Malko, C. Neiss, F. Vià ±es and A. Gà ¶rling, Phys. Rev. Lett., 2012, 108, 086804. 3.S. Zhang, J. Zhou, Q. Wang, X. Chen, Y. Kawazoe and P. Jena, Proc. Natl. Acad. Sci., 2015, 112, 2372-2377. 4.Y. Liu, G. Wang, Q. Huang, L. Guo and X. Chen, Phys. Rev. Lett., 2012, 108, 225505. 5.L. Xu, R. Wang, M. Miao, X. Wei, Y. Chen, H. Yan, W. Lau, L. Liu and Y. Ma, Nanoscale, 2014, 6, 1113-1118. 6.K. S. Novoselov, A. K.

Ancient Indian Architecture :: Papers

Ancient Indian Architecture The Science of Architecture and Civil Construction was known in Ancient India as Sthapatya-Shastra. The word Sthapatya is derived from the root word Sthapana i.e. 'to establish'. The technique of architecture was both a science and an art, hence it is also known as Sthapatya-kala, the word Kala means an art. From very early times the construction of temples, palaces, rest houses and other civil construction was undertaken by professional architects known as Sthapati. Even during the Vedic times, there existed professionals who specialized in the technique of constructing chariots and other heavy instruments of war. These professionals have been referred to in the Rig Veda as Rathakara which literally means 'chariot maker'. The excavations of the ruins at Mohenjodaro and Harrappa (today in Pakistan) proved the existence of a developed Urban civilization in India. The Indus valley civilization is dated around 3000 B.C. Thus since the last 5000 years. India has had an urban civilization. The existence of an urban civilization presumes the existence of well developed techniques of architecture and construction. These techniques would no doubt have had been systematically stated in record books for transmitting them to the later generations as well for being used as reference media for actual construction. Unfortunately, as far as the Indus Valley civilization goes no such records have been preserved either as rock edicts, manuscripts, etc., or in folk tales and legends. But the fact that cities on the scale of Mohenjodaro had been constructed bear testimony to the existence of a systematized and highly developed technique of architecture 5000 years ago. But in the later ages, from about the 7th century B.C., we have both literature references as well as archeological evidences to prove the existence of large urban civilizations in the Ganges Valley. Like in most other sciences, even remotely connected with religion, in architecture also the scientific ideas and techniques have been integrated with philosophy and theology. This was so as the majority of the large constructions were temples.

Alcoholism - No Easy Solution Essay examples -- Argumentative Persuasi

Alcoholism - No Easy Solution Mike Brake’s â€Å"Needed: A License to Drink† is a well-written essay that covers the serious issue of alcoholism and goes on to offer a creative proposal to solve the situation. Brake addresses alcoholism as a â€Å"primary public health-problem† which holds merit, considering Brake sites alcohol is the cause of 19,000 auto fatalities each year. To remedy these preventable fatalities, Brake proposes to institute a national system of licensing with appropriate penalties for violators. He goes on to say that these licenses should be issued the same way as driver’s licenses. An applicant would have to read a manual, and take a written exam which would include questions such as â€Å"How many drinks would it take to intoxicate a 150lb man?† and â€Å"What is the penalty for drunk driving?† After passing the written test applicants would be issued a drinking license that would be required for buying any alcoholic drink. Brake bases his credibility on the tragic premature loss of four family members due to alcoholism which he refers to as a â€Å"deadly disease† (Brake 135). And although it would never be acceptable to wish such terror on anyone, the misfortune is not enough to qualify a person as an expert. Brake presents strong family values and plays into the reader’s compassion for loved ones. Brake also spent two years working as a counselor in a chemical-dependency treatment center, where he gained first hand experience working with a young man who passed out while smoking and a nurse who lost her license and became a prostitute. However he mistakenly forgets the patient explanation as to why a young man who passed out while smoking and a nurse who turned prostitute, is relevant to the problem of alcoholism. If ... ... can not present a legitimate argument, second alcoholism is not a disease and so each person must find it in themselves to stop, or they have family that really loves them and help them stop. Third it would cause more problems then it is solving, and finally it would cost the general public more money then it is worth. Works Cited. Brake, Mike. "Needed: A License to Drink." The Genre of Argument. Ed. Rosenberg. Boston, MA: Thomson Heinle, March 14, 1994. 135-136. Falcone, Timothy J. "Alcoholism and Drug Addiction FAQ's Saint Jude Retreat House. 19 April 2004. Online. Internet. 19 April 2004. Available: http://www.soberforever.net/FAQ1.cfm. "National Highway Traffic Saftey Administration." Operating Administrations, U.S. DOT FY 2005 Budget in Brief. 19 April 2004. Online. Internet. 19 April 2004. Available: http://www.dot.gov/bib2005/admins.html#nhtsa.

Psychology and Best Friends

What is you most prized possession? A prized possession is something that makes you happy the most above all else. Your most prized possession can be an item or a person. One of my most prized possessions would be my best friends, because they are what makes us believe in ourselves, make one of the biggest influences in life, and let us have the ability to stay strong. Without our best friends I would not be the same person I am today. Our mental and physical abilities are essential in life, it can build us strive and become driven into our success.People should not be dependent on computers because, this can damage a person’s mental and physical ability. It can affect someone physically by having the habit of bad postures, back/neck aches, and eye pain. These body parts are essential for us to live comfortably and be able to work efficiently. Also it can affect a person’s mental health, some of the different causes are, poor concentration, poor attention span, not bein g able to multi task, no use of own knowledge, as well as sleeping disorders.If This possession is more valuable to me than other possessions because, this is what brings us happiness for me and for everyone. Best friends support us and are what help us to move forward in life. This possession is something that anybody can receive but only in one condition, show different character traits so that he or she will give you the same respect. I need this possession because whenever we are feeling down, I can depend on my friends easily.

Obama’s Commencement Speech

Obama’s Speech Everybody knows how good of a speaker Obama is. His speeches always seem to convince the audience, but it is not by everybody understood what distinguishes him from other speakers. Certain skills he frequently uses help him reach his main purpose, but the question remains what these skills include. Therefore, the aim of this commentary is explain how the use of rhetorical devices makes Obama’s speeches stand out and memorable. Rhetorical devices are techniques that an author or speaker uses in order to convey the listener or reader a message with the goal to persuade him or her towards a certain perspective.There are a lot of different kinds of techniques such as irony and the use of metaphors. When listening carefully to Obama’s speeches one is able to distinguish certain rhetorical devices that seem to keep coming back in every other of his speeches. We could say Obama has got some favourite techniques which clearly seem to help him in giving exc ellent speeches. When we take a closer look at Obama’s commencement speech for the Illinois university school of medicine we can also find the devices that keep coming back. The Technique he uses the most frequently is the so called ‘tricolon’, which can also be called ‘the rule of threes’.Tricolon uses series of three to emphasis certain issues and by this making his point even more clear and memorable. In Obama’s Inauguration speech alone we are able to find twenty two example of tricolon and in this commencement speech he also is not ‘afraid’ of using it. Already in his first sentence we are able to find an example of this device: â€Å"After four years of endless work, sleepless nights, and constant stress†. And even though this is his first sentence and it is a joke, he already stresses the fact that his audience has worked hard and that it is something they can be proud of.Also by using three word groups each from a n oun and an adjective he makes the ‘situation’ seem even more dramatic and funny. Another example when he uses tricolon is â€Å"genocide in Dafur or the AIDS epidemic or the fifteen-year-old who was gunned down on front of his house. † By using three examples instead of two or four examples he reaches the just the right point where people will get his point, understand him, where they have had enough time to think about the situation, are able to identify and keep remembering his words.There are many more great examples but tricolon is of course not the only rhetorical device he uses. Barack Obama also knows exactly how to use the pronouns ‘I’, ‘you’ and ‘we’ in a good and effective manner. By using specifically these three pronouns much more often than pronouns such as she, he or they, he is able to create a higher degree of intimacy and solidarity towards his audience. He makes his audience feel as if he is talking to them personally even though he may be speaking to an audience of thousands of people.Also when his topics concern some issues such as the health care issue in this speech, he is able to twist his story in such a way that he really believes that there is a solution and that certainly together we can always come to a solution. It is amazing he is able to tell it in such a way that the audience is also going to believe it. â€Å"This is why we need you. We need you to dream, we need you to speak out, and we need you to act. And together, we can build a health care system in this country that finally works for every American. This part of his speech is a perfect example where all of the most important rhetorical devices come together and work effectively together. We can identify his use of pronouns, tricolon (â€Å"We need you to dream, we need you to speak out, and we need you to act. †) and also anaphora. Anaphora is another of Obama’s favourite techniques. â€Å"We need you† is already repeated four times in just two sentences. The five following paragraphs also consist of anaphora, because they all begin with â€Å"We can (have)†¦Ã¢â‚¬  Repeating this part of the sentence does not only give the speech a nice structure, it is much more than that.It is saying in an indirect way that we really, honestly can, but in a much more effective way. Because every time the audience is reminded of that ‘fact’ and when things keep coming back one will be able to remember it easily with the effect that one can also start to believe in his words. â€Å"Perhaps you will first notice when a doctor tells a woman that her husband will need a life-saving procedure that their insurance does not cover and their family cannot afford. Perhaps it will be the late-stage diagnosis of a cancer that could have been prevented with a routine of screening that the patient’s health care plan just doesn’t cover.Perhaps it will be the endless stream of people who wait and wait in the emergency room which is the only place that will treat the uninsured. † Is another example were anaphora and tricolon are combined to create a stronger effect. Again three examples are used together to increase the power of the three separate examples another thing is that all three examples start with â€Å"perhaps† which is used to link the three separate examples but also again to make it more memorable. So Obama knows exactly how to use words in order to create the effect he likes: being persuasive, personal and productive.Every speaker has got his or her own characteristics in their way of speaking and so does Obama. His good and effective way of speaking distinguishes him from others. He is able to create this effectiveness by the use of important rhetorical devices. The three most important devices he uses Obama uses are tricolon, the correct use of pronouns and anaphora. By using these both separate as together he is ab le to make speeches in which his message comes across at the good manner and he is able to make speeches in which he can be as effective and persuasive as possible. 1. 058 words

Consequences of Unethical Behavior Essay

I had not heard of this until now, actually. Google paid their way out of CEO prosecution last year. Not only was their behavior unethical, and illegal, it was very socially irresponsible to the American people. Google was taking part in advertising narcotics and other prescription drugs for an illegal Canadian pharmacy on the American internet; making all of these drugs readily available to the American people. David Whitaker, a federal inmate and convicted con-artist became posed as an American government agent who went undercover to prove Google knew exactly what was going on. Google advertisement executives accepted the $200,000 worth of the government’s â€Å"set-up† money to begin advertising. Whitaker collected emails and recorded calls to prove that Google knew what they were doing were illegal. Even though it was obvious through the evidence to see that Google representatives knew that the advertisements were illegal, they extended Whitaker a â€Å"very generous credit line and allowed me to set my target advertising directly to American consumers. On August 24th, 2011, Google paid $500M dollars to pay their fines and avoid prosecution of their C. E. O. Larry Page. Through the emails and recordings, it is made obvious that Page knew exactly what was going on. Google was allowing illegal Canadian pharmacies to platform their ads on Google and target the American population. Google allowing American consumers to be targeted is absolutely outrageous. Google’s $500M fine covers the advertising costs and profits of the companies. The Department of Justice also has a â€Å"non-prosecution† agreement with Google. Now, what exactly is a â€Å"non-prosecution† agreement? To me, this all sounds like something illegal all the way around. How can a company, any company, buy their way out of prosecution? How can a C. E. O. not be classified as a drug peddler who well knows of what is going on within his company? How does this make him any different that Bernie Madoff or the Goldman Sachs C. E. O.? Google was allowing drugs to be sold through their network, period point blank; with the citizens of America being the target. How can a company buy their way out of prosecution? I just do not understand. If I was caught selling drugs, or giving people a platform to sell, I would be prosecuted to the fullest extent. Would I be able to buy my way out of prosecution? I absolutely would not! The American government would lock me away and take their sweet time about taking me to trial and finishing my case. Why was this not made more public? Now, it seems, Google is being looked into from every aspect, in which they should.

A Dirty Job Chapter 21

21 COMMON COURTESY Charlie was torn – he really wanted to take his sword-cane, but he couldn't carry it while using the crutches. He considered duct-taping it to one of the crutches, but he thought that might attract attention. â€Å"You want me to go with you?† Ray asked. â€Å"I mean, you okay to drive, with your leg and all?† â€Å"I'll be fine,† Charlie said. â€Å"Someone needs to watch the store.† â€Å"Charlie, before you go, can I ask you something?† â€Å"Sure.† Don't ask, don't ask, don't ask, Charlie thought. â€Å"Why did you need me to find these two women?† You robot-necked bastard, you had to ask. â€Å"I told you, estate stuff.† Charlie shrugged. No big deal, let it go, nothing to see here. â€Å"Yeah, I know you told me that, and normally that would make sense, but I found out a lot about these two while looking for them – no one in either of their families has died recently.† â€Å"Funny thing,† Charlie said, juggling his keys, the cane, his date book, and his crutches by the back door. â€Å"Both bequests were from nonrelatives. Old friends.† No wonder women don't like you, you just won't leave things alone. â€Å"Uh-huh,† Ray said, unconvinced. â€Å"You know, when people run, when they go as far as faking their own death to get away, they are usually running from something. Are you that something, Charlie?† â€Å"Ray, listen to yourself. Are you back on your serial-killer thing? I thought Rivera explained that.† â€Å"So this is for Rivera?† â€Å"Let's say he's interested,† Charlie said. â€Å"Why didn't you just say so?† Charlie sighed. â€Å"Ray, I'm not supposed to talk about this stuff, you know that. Fourth Amendment and all. I came to you because you're good, and you have contacts. I depend on you and I trust you. I think you know that you can depend on me and trust me, right? I mean, in all these years, I've never put your disability pension in jeopardy by being careless about our arrangement, have I?† It was a threat, however subtle, and Charlie felt bad for doing it, but he just couldn't let Ray continue to push on this, particularly since he was in unexplored territory himself – he didn't even know what kind of bluff he was covering. â€Å"So Mrs. Johnson isn't going to end up dead if I find her for you?† â€Å"I will not lay a hand on Mrs. Johnson or Mrs. Pojo†¦Mrs. Pokojo – or that other woman either. You have my word on it.† Charlie raised his hand as if swearing on a Bible and dropped one of his crutches. â€Å"Why don't you just use the cane?† Ray said. â€Å"Right,† Charlie said. He leaned the crutches on the door and tried his weight on the bad leg and the cane. The doctors had, indeed, said that it was just a flesh wound, so there was no tendon damage, just muscle, but it hurt like hell to put any weight on that foot. The cane would work, he decided. â€Å"I should be back to relieve you before five.† He limped out the door. Ray didn't like being lied to. He'd had quite enough of that from his desperate Filipinas and was becoming sensitive about being taken for a fool. Who did Charlie Asher think he was fooling? As soon as he got the store squared away, he'd give Rivera a call and see for himself. He went out into the store and did a little dusting, then went to Charlie's â€Å"special† rack, where he kept the weird estate items that he made such a fuss about. You were only supposed to sell one to each customer, but Ray had sold five of them to the same woman in the last two weeks. He knew he should have said something to Charlie, but really, why? Charlie wasn't being open with him about anything, it seemed. Besides, the woman who bought the stuff was cute, and she'd smiled at Ray. She had nice hair, a cute figure, and really striking light blue eyes. Plus there was something about her voice – she seemed so, what? Peaceful, maybe. Like she knew that everything was going to be okay and no one needed to worry. Maybe he was projecting. And she didn't have an Adam's apple, which was a big plus in Ray's book lately. He'd tried to get her name, even get a look at something in her wallet, but she'd paid in cash and had been as careful as a poker player covering her cards. If she'd driven, she'd parked too far away for him to see her get into her car from the store, so there was no license number to trace. He resolved to ask her name if she came in today. And she was due to come in. She only came in when he was working alone. He'd seen her check through the window once when he was working with Lily, and only came into the store later when Lily was gone. He really hoped she'd come in. He tried to calm himself down for his call to Rivera. He didn't want to seem like a rube to a guy who was still on the job. He used his own cell phone for the call so Rivera would see it was him calling. Charlie didn't like leaving Sophie for this long, given what had happened a few days ago, but on the other hand, whatever might be threatening her was obviously being caused by his missing these two soul vessels. The quicker he fixed the problem, the quicker the threat would be diminished. Besides, the hellhounds were her best defense, and he'd given express instructions to Mrs. Ling that the dogs and Sophie were not to be separated for any amount of time, for any reason. He took Presidio Boulevard through Golden Gate Park into the Sunset, reminding himself to take Sophie to the Japanese Tea Garden to feed the koi, now that her plague on pets seemed to have subsided. The Sunset district lay just south of Golden Gate Park, bordered by the American Highway and Ocean Beach on the west, and Twin Peaks and the University of San Francisco on the east. It had once been a suburb, until the city expanded to include it, and many of its houses were modest, single-story family dwellings, built en masse in the 1940s and '50s. They were like the mosaics of little boxes that peppered neighborhoods across the entire country in that postwar period, but in San Francisco, where so much had been built after the quake and fire of '06, then again in the economic boom of the late twentieth century, they seemed like anachronisms from both ends of time. Charlie felt like he was driving through the Eisenhower era, at least until he passed a mother with a shaved head and tribal tattoos on her scalp pushing twins in a double stroller. Irena Posokovanovich's sister lived in a small, one-story frame house with a small covered porch that had jasmine vines growing up trellises on either side and springing off into the air like morning-after-sex hair. The rest of the tiny yard was meticulously groomed, from the holly hedge at the sidewalk to the red geraniums that lined the concrete path up to the house. Charlie parked a block away and walked to the house. On the way he was nearly run over by two different joggers, one a young mother pushing a running stroller. They couldn't see him – he was on track. Now, how to go about getting in? And then what? If he was the Luminatus, then perhaps just his presence would take care of the problem. He checked around back and saw that there was a car in the garage, but the shades were drawn on all the windows. Finally he decided on the frontal approach and rang the doorbell. A few seconds later a short woman in her seventies wearing a pink chenille housecoat opened the door. â€Å"Yes,† she said, looking a little suspicious as she eyed Charlie's walking cast. She quickly flipped the lock on the screen door. â€Å"Can I help you?† It was the woman in the picture. â€Å"Yes, ma'am, I'm looking for Irena Posokovanovich.† â€Å"Well, she's not here,† said Irena Posokovanovich. â€Å"You must have the wrong house.† She started to close the door. â€Å"Wasn't there a death notice in the paper a couple of weeks ago?† Charlie said. So far, his awesome presence as the Luminatus wasn't having much of an effect on her. â€Å"Well, yes, I believe there was,† said the woman, sensing an out. She opened the door a little more. â€Å"It was such a tragedy. We all loved Irena so much. She was the kindest, most generous, most loving, attractive – you know, for her age – well-read – â€Å" â€Å"And evidently didn't know that it's considered common courtesy when you publish a death notice to actually die!† Charlie held out the enlarged driver's-license picture. He considered adding aha! but thought that might be a little over-the-top. Irena Posokovanovich slammed the door. â€Å"I don't know who you are, but you have the wrong house,† she said through the door. â€Å"You know who I am,† Charlie said. Actually, she probably had no idea who he was. â€Å"And I know who you are, and you are supposed to have died three weeks ago.† â€Å"You're mistaken. Now go away before I call the police and tell them that there's a rapist at my door.† Charlie gagged a little, then pushed on. â€Å"I am not a rapist, Mrs. Poso†¦Posokev – I'm Death, Irena. That's who I am. And you are overdue. You need to die, this minute if possible. There's nothing to be afraid of. It's like going to sleep, only, well – â€Å" â€Å"I'm not ready,† Irena whined. â€Å"If I was ready I wouldn't have left my home. I'm not ready.† â€Å"I'm sorry, ma'am, but I have to insist.† â€Å"I'm sure you're mistaken. Perhaps another Mrs. Posokovanovich.† â€Å"No, here it is, right here in the calendar, with your address. It's you.† Charlie held his date book turned to the page with her name on it up to the little window in the door. â€Å"And you say that that is Death's calendar?† â€Å"That's correct, ma'am. Notice the date. And this is your second notice.† â€Å"And you are Death?† â€Å"That's right.† â€Å"Well, that's just silly.† â€Å"I am not silly, Mrs. Posokovanovich. I am Death.† â€Å"Aren't you supposed to have a sickle and a long black robe?† â€Å"No, we don't do that anymore. Take my word for it, I am Death.† He tried to sound really ominous. â€Å"Death is always tall in the pictures.† She was standing on tiptoe, he could tell the way she kept bouncing up by the little window to get a look at him. â€Å"You don't seem tall enough.† â€Å"There's no height requirement.† â€Å"Then could I see your business card?† â€Å"Sure.† Charlie took out a card and held it against the glass. â€Å"This says ‘Purveyor of Fine Vintage Clothing and Accessories.'† â€Å"Right! Exactly!† He knew he should have had a second set of business cards printed up. â€Å"And where do you think I get those things? From the dead. You see?† â€Å"Mr. Asher, I'm going to have to ask you to leave.† â€Å"No, ma'am, I'm going to have to insist that you pass away, this instant. You're overdue.† â€Å"Go away! You are a charlatan, and I think you need psychological help.† â€Å"Death! You're fucking with Death! Capital D, bitch!† Well, that was uncalled for. Charlie felt bad the second he said it. â€Å"Sorry,† he mumbled to the door. â€Å"I'm calling the police.† â€Å"You go ahead, Mrs. – uh – Irena. You know what they'll tell you, that you're dead! It was in the Chronicle. They hardly ever print stuff that's not true.† â€Å"Please go away. I practiced for a long time so I could live longer, it's not fair.† â€Å"What?† â€Å"Go away.† â€Å"I heard that part, I mean the part about practicing.† â€Å"Never you mind. You just go take someone else.† Charlie actually had no idea what he would do if she let him in. Maybe he had to touch her for his Death abilities to kick in. He remembered seeing an old Twilight Zone as a kid, where Robert Redford was Death, and this old lady wouldn't let him in, so he pretended to be injured, and when she came to help him†¦ALA-KAZAM! She croaked, and he peacefully led her off to Hole in the Wall, where she helped him produce independent movies. Maybe that would work. He did have the cast and the cane going for him. He looked up and down the street to make sure that no one could see him, then he lay down, half on the little porch, half on the concrete steps. He threw his cane against the door and made sure that it clattered loudly on the concrete, then he let out what he thought was a very convincing wail. â€Å"Ahhhhhhhhh, I've broken my leg.† He heard footsteps inside and saw gray hair at the little window, bouncing a little so she could see out. â€Å"Oh, it hurts,† Charlie wailed. â€Å"Help.† More steps, the shade in the window to the right of the door parted and he saw an eye. He grimaced in fake pain. â€Å"Are you all right?† said Mrs. Posokovanovich. â€Å"I need help. My leg was hurt before, but I slipped on your steps. I think I've broken something. There's blood, and a piece of bone sticking out.† He kept his leg below the level where she could see it. â€Å"Oh my,† she said. â€Å"Give me a minute.† â€Å"Help. Please. The pain. So – much – pain.† Charlie coughed the way cowboys do when they are dying in the dirt and things are getting all dark. He heard the latch being thrown, and then the inner door opened. â€Å"You're really hurt bad,† she said. â€Å"Please,† Charlie said, holding his hand out to her. â€Å"Help me.† She unlatched the screen. Charlie suppressed a grin. â€Å"Oh, thank you,† he gasped. She threw open the screen door and blasted him in the face with a stream of pepper spray. â€Å"I saw that Twilight Zone, you son of a bitch!† The doors slammed. The latch was thrown. Charlie's face felt like it was on fire. When he could finally see well enough to walk, as he limped back to his van, he heard a female voice say, â€Å"I'd have let you in, lover.† Then a chorus of spooky-girlish laughter erupted from the storm sewer. He backed against the van, ready to draw the sword from the cane, but then he heard what sounded like a small dog barking in the sewer. â€Å"Where did he come from?† said one of the harpies. â€Å"He bit me! You little fucker!† â€Å"Get him!† â€Å"I hate dogs. When we take over, no dogs.† The barking faded away, followed by the voices of the sewer harpies. Charlie took a deep breath and tried to blink the pain out of his eyes. He needed to regroup, but then he was taking the old lady down, pepper spray or not. It took him the better part of an hour to get into position, but once he was ready, he put down the cinder block, flipped open his cell phone, and dialed the number he'd gotten from information. A woman answered. â€Å"Hello.† â€Å"Ma'am, this is the gas company,† Charlie said in his best gas-company voice. â€Å"My grid is showing pressure loss at your address. We're sending a truck right out, but you need to get everyone out of the house, right now.† â€Å"Well, I'm the only one here right now, but I'm sorry, I don't smell gas.† â€Å"It may be building up under the house,† Charlie said, feeling proud of himself for being quick on his feet. Is there anyone else in the house?† â€Å"No, just me and my kitty, Samantha.† â€Å"Ma'am, please take the cat and go out by the street. Our truck will meet you there. Go right now, okay?† â€Å"Well, all right.† â€Å"Thank you, ma'am.† Charlie clicked off. He could feel movement inside of the house. He moved right to the edge of the porch roof and raised the concrete cinder block over his head. It'll look like an accident, he thought, like a cinder block fell off the porch roof. He was glad that no one could see him up here. He was sweating from the climb, his armpits stained, his trousers wrinkled. He heard the door open and got ready to throw the cinder block as soon as his target emerged from under the roof. â€Å"Good afternoon, ma'am.† A man's voice, out by the street. Charlie looked down to see Inspector Rivera standing at the sidewalk, having just climbed out of an unmarked car. What the hell was he doing here? â€Å"Are you the gas company?† said Mrs. Posokovanovich. â€Å"No, ma'am, I'm from the San Francisco police.† He flashed his badge. â€Å"They told me there was a gas leak,† she said. â€Å"That's been taken care of, ma'am. Could you step back inside and I'll check with you in a minute, okay?† â€Å"Well, okay, then.† Charlie heard the doors open and close again. His arms were trembling from holding the cinder block over his head. He tried to breathe quietly, thinking that the sound of his wheezing might attract Rivera's attention, make him visible. â€Å"Mr. Asher, what are you doing up there?† Charlie nearly lost his balance and went over. â€Å"You can see me?† â€Å"Yes, sir, I certainly can. And I can also see that cinder block you're holding over your head.† â€Å"Oh, this old thing.† â€Å"What were you planning on doing with that?† â€Å"Repairs?† Charlie tried. How could Rivera see him when he was in soul-vessel-retrieval mode? â€Å"I'm sorry, but I don't believe you, Mr. Asher. You're going to have to drop the cinder block.† â€Å"I'd rather not. It was really hard getting it up here.† â€Å"Be that as it may, I'm going to have to insist that you drop it.† â€Å"I was planning on it, but then you showed up.† â€Å"Please. Indulge me. Look, you're sweating. Climb down and you can sit in my air-conditioned car with me. We'll chat – talk about Italian suits, the Giants – I don't know – why you were about to brain that sweet old lady with a cinder block. Air-conditioning, Mr. Asher – won't that be nice?† Charlie brought the cinder block down and rested it on his thigh, feeling his trousers snagging beyond repair as he did so. â€Å"That's not much of an incentive. What am I, some primitive Amazon native? I've had air-conditioning before. I have air-conditioning in my own van.† â€Å"Yes, I'll admit it's not exactly a weekend in Paris, but the next choice was that I shoot you off the roof, and they put you in a body bag, which is going to be sweltering on a warm day like this.† â€Å"Oh, well, yes,† Charlie said. â€Å"That does make air-conditioning sound a lot more inviting. Thanks. I'm going to toss my brick down first, if that's okay?† â€Å"That would be great, Mr. Asher.† Disillusioned with DesperateFilipinas, Ray was browsing through the selection of lonely first-grade teachers with master's degrees in nuclear physics on when she came through the door. He heard the bell and caught her out of the corner of his eye, and forgetting that his neck vertebrae were fused, he sprained the left side of his face trying to turn to see her. She saw him looking and smiled. Ray smiled back, then, out of the corner of his eye, saw the monitor with the photo of the first-grade teacher holding her breasts, and sprained the right side of his face trying to turn in time to punch the power button before she passed the counter. â€Å"Just browsing,† said the love of his life. â€Å"How are you today?† â€Å"Hi,† Ray said. In his mental rehearsals, he started with â€Å"hi,† and it just sort of burped out of him before he realized that it put him behind a beat. â€Å"I mean, fine. Sorry. I was working.† â€Å"I can see that.† Again the smile. She was so understanding, forgiving – and kind, you could just tell that by her eyes. He knew in his heart that he would even sit through a hat movie for this woman. He would watch A Room with a View AND The English Patient, back-to-back, just to share a pizza with her. And she would stop him from eating his service revolver halfway through the second movie, because that's just how she was: compassionate. She made a show of browsing the store, but two minutes hadn't passed before she made for Charlie's special shelf. Even the sign said SPECIAL ITEMS – ONE PER CUSTOMER, but it didn't say if that was a per-day policy, or one per lifetime. Charlie hadn't really specified, now that Ray thought about it. Sure, Lily had yammered on about how important it was that they adhere to the policy, but that was Lily, she might have grown up some, but she was still disturbed. After a short time she picked up an electric alarm clock and brought it over to the counter. This was it. This was it. Ray heard the back door open. â€Å"Will this be everything?† he said. â€Å"Yes,† said the future Mrs. Ray Macy. â€Å"I've been looking for one like this.† â€Å"Yep, you can't beat a Sunbeam,† Ray said. â€Å"That's two-sixteen with tax – aw, heck, call it two even.† â€Å"That's very nice of you,† she said, digging into a small purse woven from colorful Guatemalan cotton thread. â€Å"Hi, Ray,† Lily said, suddenly standing there beside him like some evil phantom who appeared out of nowhere to leech every potentially joyous moment out of his life. â€Å"Hi, Lily,† he said. Lily clicked some keys on the computer. Slowed down by his freshly sprained face, Ray wasn't able to turn before she'd hit the power button on the monitor. â€Å"What's this?† asked Lily. With his free hand, Ray thumped Lily in the thigh under the counter. â€Å"Ouch! Freak!† â€Å"I'm sure you'll enjoy waking up with that,† Ray said, handing the alarm clock to the woman who would be his queen. â€Å"Thank you so much,† said the lovely brunette goddess of all things Ray. â€Å"By the way,† Ray said, pushing on, â€Å"you've been in a couple of times, I was wondering, you know, because I'm curious that way, uh, what's your name?† â€Å"Audrey.† â€Å"Hi, Audrey. I'm Ray.† â€Å"Nice to meet you, Ray. Gotta go. Bye.† She waved over her shoulder and headed out the door. Ray and Lily watched her walk away. â€Å"Nice butt,† Lily said. â€Å"She said my name,† Ray said. â€Å"She's a little bit – I don't know – unimaginary for you.† Ray turned to the nemesis Lily. â€Å"You have to watch the store. I have to go.† â€Å"Why?† â€Å"I have to follow her, find out who she is.† Ray began to gather his stuff – phone, keys, baseball cap. â€Å"Yeah, that's healthy, Ray.† â€Å"Tell Charlie I – don't tell Charlie.† â€Å"Okay. So is it okay if I switch the computer from the UGLY Web site?† â€Å"What are you talking about?† Lily stepped back from the screen and pointed to the letters as she read, â€Å"Ukrainian Girls Loving You – U-G-L-Y, ugly.† Lily smiled, a perky, self-satisfied smile, like that kid who won the spelling bee in third grade. Didn't you hate that kid? Ray couldn't believe it. They weren't even being subtle about it anymore. â€Å"Can't talk,† he said. â€Å"Gotta go.† He ran out the door and headed up Mason Street after the lovely and compassionate Audrey. Rivera had driven up to the Cliff House Restaurant overlooking Seal Rocks and forced Charlie to buy him a drink while they watched the surfers down on the beach. Rivera was not a morbid man, but he knew that if he came here enough times, eventually he'd see a surfer get hit by a white shark. In fact, he sorely hoped that it would happen, because otherwise, the world made no sense, there was no justice, and life was just a tangled ball of chaos. Thousands of seals in the water and on the rocks – the mainstay of the white shark diet – hundreds of surfers in the water, dressed like seals, well, it just needed to happen for all to be right with the world. â€Å"I never believed you, Mr. Asher, when you said that you were Death, but since I couldn't explain whatever that thing was in the alley with you, didn't want to explain, in fact, I let it slide.† â€Å"And I appreciate that,† said Charlie, showing a little discomfort at drinking a glass of wine with handcuffs on. His face was candy-apple red from having been burned by the pepper spray. â€Å"Is this normal procedure for interrogations?† â€Å"No,† Rivera said. â€Å"Normally the City is supposed to pay, but I'll have the judge take the drinks off your sentence.† â€Å"Great. Thanks,† Charlie said. â€Å"And you can call me Charlie.† â€Å"Okay, and you can call me Inspector Rivera. Now, braining the old lady with the cinder block – just exactly what were you thinking?† â€Å"Do I need a lawyer?† â€Å"Of course not, you're fine, this bar is full of witnesses.† Rivera had once been a by-the-book kind of cop. That was before the demons, the giant owls, the bankruptcy, the polar bears, the vampires, the divorce, and the saber-clawed woman-thing that turned into a bird. Now, not so much. â€Å"In that case, I was thinking that no one could see me,† Charlie said. â€Å"Because you were invisible?† â€Å"Not really. Just sort of not noticeable.† â€Å"Well, I'll give you that, but I don't think that's any reason to crush a grandmother's skull.† â€Å"You have no proof of that,† Charlie said. â€Å"Of course I do,† Rivera said, holding up his glass to signal to the waitress that he needed another Glenfiddich on the rocks. â€Å"I saw pictures of her grandchildren, she showed me when I went in the house.† â€Å"No, I mean you have no proof that I was going to crush her skull.† â€Å"I see,† said Rivera, who did not see at all. â€Å"How did you know Mrs. Posokovanovich?† â€Å"I didn't. Her name just showed up in my date book, like I showed you.† â€Å"Yes, you did. Yes, you did. But that doesn't really give you a license to kill her, now does it?† â€Å"That's the point, she was supposed to be dead three weeks ago. There was even a death notice in the paper. I was just trying to make sure it was accurate.† â€Å"So in lieu of having the Chronicle print a correction, you thought you'd bash in granny's brains.† â€Å"Well, it was that or have my daughter say ‘kitty' at her, and I refuse to exploit my child in that way.† â€Å"Well, I admire your taking the high ground on that one, Charlie,† Rivera said, thinking, Who do I have to shoot to get a drink around here? â€Å"But let's just say that for one millisecond I believe you, and the old lady was supposed to die, but didn't, and that because of it you were shot with a crossbow and that thing I shot in the alley appeared – let's just say I believe all that, what am I supposed to do about it?† â€Å"You need to be careful,† Charlie said. â€Å"You may be turning into one of us.† â€Å"Pardon?† â€Å"That's how it happened to me. When my wife passed away, in the hospital, I saw the guy that came to collect her soul vessel, and wham, I was a Death Merchant. You saw me today, when no one else could, and you saw the sewer harpy, that night in the alley. Most of the time, I'm the only one who can see them.† Rivera really, really wanted to turn this guy over to a psychiatrist at the hospital and never see him again, but the problem was, he had seen the woman-thing, that night and another time on his own street, and he had seen reports of weird stuff happening in the City over the last two weeks. And not just normal San Francisco weird stuff, but really weird stuff, like a flock of ravens attacking a tourist in Coit Tower, and a guy who slammed his car through a storefront in Chinatown, saying that he had swerved to miss a dragon, and people all over the Mission saying that they'd seen an iguana dressed like a musketeer going through their garbage, tiny sword and all. â€Å"I can prove it,† Charlie said. â€Å"Just take me to the music store in the Castro.† Rivera looked at the sad, naked ice cubes in his glass and said, â€Å"Anyone ever tell you that it's hard to follow your train of thought, Charlie?† â€Å"You need to talk to Minty Fresh.† â€Å"Of course, that clears things up. I'll have a word with Krispy Kreme while I'm there.† â€Å"He's also a Death Merchant. He can tell you that what I'm telling you is true and you can let me go.† â€Å"Get up.† Rivera stood. â€Å"I'm not finished with my wine.† â€Å"Leave the money for the drinks and get up, please.† Rivera hooked his finger in Charlie's handcuffs and pulled him up. â€Å"We're going to the Castro.† â€Å"I don't think I can work my cane with these things on,† Charlie said. Rivera sighed and looked down on the surfers. He thought he saw something large moving in a wave behind one surfer, but as his heart leapt at the prospect, a sea lion poked his whiskered face out of the curl and Rivera's spirits sank again. He threw Charlie the handcuff keys. â€Å"Meet me in the car, I have to take a leak.† â€Å"I could escape.† â€Å"You do that, Charlie – after you pay.†