Thermally induced chemistry and electron-mediated processes of pyridine on (2×1) and modified Si() surfaces: evidence of electron-induced condensation oligomerization

Li, Q; Leung, K. T.

doi:10.1016/s0039-6028(03)00890-2

Cited by 24 publications

(41 citation statements)

References 44 publications

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“…Their datively-bonded structure (figure 1 in [15]) is symmetrically constrained and hence not a true minimum. We compared this constrained configuration to the fully-relaxed configuration (figure 3(a)) and found 6 that the 6 Using a two-row, six-dimer cluster Si 75 H 56 , the extended basis set (see text), and the same GGA functional (PBE) as used in [15], we find that the fully asymmetric dative configuration (figure 3(a)) is 0.15 eV more stable than the C(s)-symmetric dative structure described in [15] (see figure 1 in [15] where this structure is labelled EO). Vibrational frequency calculations confirm that the symmetric dative structure is not a true minimum, but a first-order saddle point, which suggests that the authors of [15] did not examine the stability of their dative structure with respect to symmetry breaking.…”

Section: Structuresmentioning

confidence: 99%

“…The reactivity of pyridine on Si(0 0 1) has been extensively studied both experimentally [6][7][8][9][10][11][12] and theoretically [6,7,[12][13][14][15][16][17][18][19], and some of the key adsorption configurations are illustrated in figure 1 using previously unpublished scanning tunnelling microscopy (STM) images from the study described in [8]. In the initial stages of pyridine chemisorption onto Si(0 0 1) the lone pair on the nitrogen interacts with an electrophilic silicon atom to form a dative Si-N bond which preserves the aromaticity of the adsorbate.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Reaction pathways for pyridine adsorption on silicon (0 0 1)

Bennett¹,

Marks²,

Miwa³

et al. 2014

J. Phys.: Condens. Matter

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Density functional theory is used to describe the reactions of chemisorption of pyridine on the silicon (0 0 1) surface. Adsorption energies of six relevant structures, and the activation energies between them are reported. We consider in detail the dative to tight-bridge transition for which conflicting results have been reported in the literature, and provide a description of the formation of inter-row chains observed in high-coverage experiments. We demonstrate that the choice of DFT functional has a considerable effect on the relative energetics and of the four DFT functionals considered, we find that the range-separated hybrid ωB97X-D functional with empirical dispersion provides the most consistent description of the experiment data.

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Section: Structuresmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Reaction pathways for pyridine adsorption on silicon (0 0 1)

Bennett¹,

Marks²,

Miwa³

et al. 2014

J. Phys.: Condens. Matter

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show abstract

“…3.22 [252]. Upon further heating, pyridine exhibits a complex array for reactions including dissociation, fragmentation, and dissociative desorption [253]. Thus, though increased temperature favors complex interactions of pyridine with the Si(100)-2×1 substrate, lowtemperature kinetic regime may hold the key for retention of aromaticity in pyridine.…”

Section: Heteroaromatics: Aromaticity As a Driving Force In Surface Pmentioning

confidence: 99%

Chemical manipulation of multifunctional hydrocarbons on silicon surfaces

Leftwich

Teplyakov

2007

Surface Science Reports

123

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“…17 For the present TPD experiments, a home-built programmable proportional-integral-differential temperature controller was used to provide linear temperature ramping at an adjustable heating rate, typically set at 2 K/s. 10 The temperature was calibrated by the desorption of dihydride at 680 K and that of monohydride at 800 K on Si(100)2×1. 36,37 XPS spectra were collected with an acceptance angle of (4°at normal emission from the silicon sample and with a constant pass energy of 50 eV, giving an effective energy resolution of 1.4 eV full width at half-maximum (for the Si 2p photopeak).…”

Section: Experimental and Computational Detailsmentioning

confidence: 99%

Surface Chemistry of Monochlorinated and Dichlorinated Benzenes on Si(100)2×1: Comparison Study of Chlorine Content and Isomeric Effects

2006

J. Phys. Chem. B

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Using X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD), the room temperature (RT) adsorption and thermal evolution of monochlorobenzene (MCB) and 1,3-dichlorobenzene (1,3-DCB) on Si(100)2×1 have been investigated and compared with that of 1,2-dichlorobenzene (1,2-DCB) reported previously. Like 1,2-DCB, the C 1s features observed at 284.6 (C 1 ) and 286.0 eV (C 2 ) for both MCB and 1,3-DCB could be attributed to the C-H and C-Cl bonds, respectively. The C 1 /C 2 intensity ratios for MCB (5.0) and 1,3-DCB (2.0) are found to follow the stoichiometric ratios of the C-H to C-Cl bonds for MCB and 1,3-DCB, respectively, indicating that both MCB and 1,3-DCB adsorb on Si(100)2×1 molecularly with negligible C-Cl dissociation at RT, in marked contrast to the partial C-Cl dissociation found for 1,2-DCB. Unlike 1,2-DCB with two discernible Cl 2s features at 270.3 and 271.2 eV, a single Cl 2s feature at 271.2 eV is observed for MCB and 1,3-DCB, in accord with the single local chemical environment for Cl. The TPD results show that MCB undergoes molecular desorption exclusively, similar to that found for benzene. Both molecular desorption and recombinative HCl desorption are found for 1,3-DCB, similar to that for 1,2-DCB. Despite the different Cl contents and relative Cl locations on the benzene ring, both MCB and 1,3-DCB exhibit RT adsorption behavior remarkably similar to that of benzene. To explain the C-Cl dissociation observed for 1,2-DCB, we propose a possible transition state involving the Cl atoms located at more physically compatible positions with the surface Si dimers in order to facilitate the conversion of 1,2-DCB (preferentially over 1,3-DCB) to dissociated products at RT. However, the thermal evolution of 1,3-DCB is closer to that of 1,2-DCB than that of MCB and benzene. The breakage of C-Cl bonds is found to occur at a relatively low temperature of 425 K, which suggests a relatively low activation barrier for the dechlorination of 1,3-DCB adspecies. Calculated energetics for 1,4-DCB on Si(100)2×1 shows that double dechlorination is not as favorable a process as those for 1,2-DCB and 1,3-DCB.

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Thermally induced chemistry and electron-mediated processes of pyridine on (2×1) and modified Si() surfaces: evidence of electron-induced condensation oligomerization

Cited by 24 publications

References 44 publications

Reaction pathways for pyridine adsorption on silicon (0 0 1)

Reaction pathways for pyridine adsorption on silicon (0 0 1)

Chemical manipulation of multifunctional hydrocarbons on silicon surfaces

Surface Chemistry of Monochlorinated and Dichlorinated Benzenes on Si(100)2×1: Comparison Study of Chlorine Content and Isomeric Effects

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