Steric and chain length effects in the (√(3) × √(3))R30° structures of alkanethiol self-assembled monolayers on Au(111)
The translational and orientational potential energy surfaces (PESs) of n-alkanethiols with up to four carbon atoms are studied for (√(3) × √(3))R30° self-assembled monolayers (SAMs). The PESs indicate that methanethiol may form SAM structures that are not accessible for long-chain thiols. The tilt...
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- Alkanethiols
Density functional calculations
Gold
Monolayers
Structure elucidation
Atoms
Carbon
Chain length
Complexation
Crystal symmetry
Density functional theory
Dimers
Gold
Gold compounds
Molecular physics
Monolayers
Paraffins
Point defects
Potential energy
Potential energy surfaces
Quantum chemistry
Self assembled monolayers
Single crystals
Sulfur
Van der Waals forces
Alkanethiol self-assembled monolayers
Alkanethiols
Chain-chain interactions
Gradient approximation
Interaction energies
Structure elucidation
Thermal equilibriums
Van Der Waals interactions
Binding energy
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dc.title.none.fl_str_mv |
Steric and chain length effects in the (√(3) × √(3))R30° structures of alkanethiol self-assembled monolayers on Au(111) |
title |
Steric and chain length effects in the (√(3) × √(3))R30° structures of alkanethiol self-assembled monolayers on Au(111) |
spellingShingle |
Steric and chain length effects in the (√(3) × √(3))R30° structures of alkanethiol self-assembled monolayers on Au(111) Alkanethiols Density functional calculations Gold Monolayers Structure elucidation Atoms Carbon Chain length Complexation Crystal symmetry Density functional theory Dimers Gold Gold compounds Molecular physics Monolayers Paraffins Point defects Potential energy Potential energy surfaces Quantum chemistry Self assembled monolayers Single crystals Sulfur Van der Waals forces Alkanethiol self-assembled monolayers Alkanethiols Chain-chain interactions Gradient approximation Interaction energies Structure elucidation Thermal equilibriums Van Der Waals interactions Binding energy |
title_short |
Steric and chain length effects in the (√(3) × √(3))R30° structures of alkanethiol self-assembled monolayers on Au(111) |
title_full |
Steric and chain length effects in the (√(3) × √(3))R30° structures of alkanethiol self-assembled monolayers on Au(111) |
title_fullStr |
Steric and chain length effects in the (√(3) × √(3))R30° structures of alkanethiol self-assembled monolayers on Au(111) |
title_full_unstemmed |
Steric and chain length effects in the (√(3) × √(3))R30° structures of alkanethiol self-assembled monolayers on Au(111) |
title_sort |
Steric and chain length effects in the (√(3) × √(3))R30° structures of alkanethiol self-assembled monolayers on Au(111) |
dc.subject.keywords.none.fl_str_mv |
Alkanethiols Density functional calculations Gold Monolayers Structure elucidation Atoms Carbon Chain length Complexation Crystal symmetry Density functional theory Dimers Gold Gold compounds Molecular physics Monolayers Paraffins Point defects Potential energy Potential energy surfaces Quantum chemistry Self assembled monolayers Single crystals Sulfur Van der Waals forces Alkanethiol self-assembled monolayers Alkanethiols Chain-chain interactions Gradient approximation Interaction energies Structure elucidation Thermal equilibriums Van Der Waals interactions Binding energy |
topic |
Alkanethiols Density functional calculations Gold Monolayers Structure elucidation Atoms Carbon Chain length Complexation Crystal symmetry Density functional theory Dimers Gold Gold compounds Molecular physics Monolayers Paraffins Point defects Potential energy Potential energy surfaces Quantum chemistry Self assembled monolayers Single crystals Sulfur Van der Waals forces Alkanethiol self-assembled monolayers Alkanethiols Chain-chain interactions Gradient approximation Interaction energies Structure elucidation Thermal equilibriums Van Der Waals interactions Binding energy |
description |
The translational and orientational potential energy surfaces (PESs) of n-alkanethiols with up to four carbon atoms are studied for (√(3) × √(3))R30° self-assembled monolayers (SAMs). The PESs indicate that methanethiol may form SAM structures that are not accessible for long-chain thiols. The tilt of the thiol molecules is determined by a compromise between the preferred binding geometry at the sulfur atom and the steric requirements of the alkane chains. The Au-S bond lengths, offset from the bridge position (brg), and the Au-S-C bond angles result in tilt angles of the S-C bond in the range of 55-60°. As DFT/generalized gradient approximation systematically underestimates chain-chain interactions, the binding energies are corrected by comparison to MP2 interaction energies of alkane dimers in SAM-like configurations. The resulting thiol binding energies increase by approximately 1 kcal mol-1 per CH2 group, which results in a substantial stabilization of long-chain SAMs due to chain-chain interactions. Furthermore, as the chain length increases, the accessible range of backbone tilt angles is constrained due to steric effects. The combination of these two effects may explain why SAM structures with long-chain thiols exhibit higher order in experiments. For each thiol two favorable SAM structures are found with the sulfur head group at the fcc-brg and hcp-brg positions, respectively. These domains may coexist in thermal equilibrium. In combination with the symmetry of the gold (111) surface, this raises the possibility of up to six different domains on single-crystal terraces. Reconstructions by an adatom or vacancy of ethanethiol SAMs with (√(3) × √(3))R30° lattice are also studied using PES scans. The results indicate that adsorption of thiols next to a vacancy is favorable and may lead to point defects inside SAMs. Showing potential: The translational and orientational potential energy surfaces of n-alkanethiols with up to four carbon atoms are studied for (√(3) × √(3))R30° self-assembled monolayers (SAMs, see picture). The binding energies with the van der Waals interactions corrected using MP2 calculations increase by about 1 kcal mol-1 per CH2 group. This trend and the increasingly confined accessible range of the tilt angles may contribute to the higher order observed in long-chain thiol SAMs on gold. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
publishDate |
2011 |
dc.date.issued.none.fl_str_mv |
2011 |
dc.date.accessioned.none.fl_str_mv |
2020-03-26T16:32:58Z |
dc.date.available.none.fl_str_mv |
2020-03-26T16:32:58Z |
dc.type.coarversion.fl_str_mv |
http://purl.org/coar/version/c_970fb48d4fbd8a85 |
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http://purl.org/coar/resource_type/c_2df8fbb1 |
dc.type.driver.none.fl_str_mv |
info:eu-repo/semantics/article |
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info:eu-repo/semantics/publishedVersion |
dc.type.spa.none.fl_str_mv |
Artículo |
status_str |
publishedVersion |
dc.identifier.citation.none.fl_str_mv |
ChemPhysChem; Vol. 12, Núm. 5; pp. 999-1009 |
dc.identifier.issn.none.fl_str_mv |
14394235 |
dc.identifier.uri.none.fl_str_mv |
https://hdl.handle.net/20.500.12585/9113 |
dc.identifier.doi.none.fl_str_mv |
10.1002/cphc.201000803 |
dc.identifier.instname.none.fl_str_mv |
Universidad Tecnológica de Bolívar |
dc.identifier.reponame.none.fl_str_mv |
Repositorio UTB |
dc.identifier.orcid.none.fl_str_mv |
35094573000 7003439449 6701809115 |
identifier_str_mv |
ChemPhysChem; Vol. 12, Núm. 5; pp. 999-1009 14394235 10.1002/cphc.201000803 Universidad Tecnológica de Bolívar Repositorio UTB 35094573000 7003439449 6701809115 |
url |
https://hdl.handle.net/20.500.12585/9113 |
dc.language.iso.none.fl_str_mv |
eng |
language |
eng |
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Atribución-NoComercial 4.0 Internacional |
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Recurso electrónico |
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application/pdf |
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Wiley-VCH Verlag |
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Wiley-VCH Verlag |
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2020-03-26T16:32:58Z2020-03-26T16:32:58Z2011ChemPhysChem; Vol. 12, Núm. 5; pp. 999-100914394235https://hdl.handle.net/20.500.12585/911310.1002/cphc.201000803Universidad Tecnológica de BolívarRepositorio UTB3509457300070034394496701809115The translational and orientational potential energy surfaces (PESs) of n-alkanethiols with up to four carbon atoms are studied for (√(3) × √(3))R30° self-assembled monolayers (SAMs). The PESs indicate that methanethiol may form SAM structures that are not accessible for long-chain thiols. The tilt of the thiol molecules is determined by a compromise between the preferred binding geometry at the sulfur atom and the steric requirements of the alkane chains. The Au-S bond lengths, offset from the bridge position (brg), and the Au-S-C bond angles result in tilt angles of the S-C bond in the range of 55-60°. As DFT/generalized gradient approximation systematically underestimates chain-chain interactions, the binding energies are corrected by comparison to MP2 interaction energies of alkane dimers in SAM-like configurations. The resulting thiol binding energies increase by approximately 1 kcal mol-1 per CH2 group, which results in a substantial stabilization of long-chain SAMs due to chain-chain interactions. Furthermore, as the chain length increases, the accessible range of backbone tilt angles is constrained due to steric effects. The combination of these two effects may explain why SAM structures with long-chain thiols exhibit higher order in experiments. For each thiol two favorable SAM structures are found with the sulfur head group at the fcc-brg and hcp-brg positions, respectively. These domains may coexist in thermal equilibrium. In combination with the symmetry of the gold (111) surface, this raises the possibility of up to six different domains on single-crystal terraces. Reconstructions by an adatom or vacancy of ethanethiol SAMs with (√(3) × √(3))R30° lattice are also studied using PES scans. The results indicate that adsorption of thiols next to a vacancy is favorable and may lead to point defects inside SAMs. Showing potential: The translational and orientational potential energy surfaces of n-alkanethiols with up to four carbon atoms are studied for (√(3) × √(3))R30° self-assembled monolayers (SAMs, see picture). The binding energies with the van der Waals interactions corrected using MP2 calculations increase by about 1 kcal mol-1 per CH2 group. This trend and the increasingly confined accessible range of the tilt angles may contribute to the higher order observed in long-chain thiol SAMs on gold. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Recurso electrónicoapplication/pdfengWiley-VCH Verlaghttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/restrictedAccessAtribución-NoComercial 4.0 Internacionalhttp://purl.org/coar/access_right/c_16echttps://www.scopus.com/inward/record.uri?eid=2-s2.0-79953228905&doi=10.1002%2fcphc.201000803&partnerID=40&md5=1b39cf4c9196a19ed12b891ecce150cbSteric and chain length effects in the (√(3) × √(3))R30° structures of alkanethiol self-assembled monolayers on Au(111)info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArtículohttp://purl.org/coar/version/c_970fb48d4fbd8a85http://purl.org/coar/resource_type/c_2df8fbb1AlkanethiolsDensity functional calculationsGoldMonolayersStructure elucidationAtomsCarbonChain lengthComplexationCrystal symmetryDensity functional theoryDimersGoldGold compoundsMolecular physicsMonolayersParaffinsPoint defectsPotential energyPotential energy surfacesQuantum chemistrySelf assembled monolayersSingle crystalsSulfurVan der Waals forcesAlkanethiol self-assembled monolayersAlkanethiolsChain-chain interactionsGradient approximationInteraction energiesStructure elucidationThermal equilibriumsVan Der Waals interactionsBinding energyTorres E.Blumenau A.T.Biedermann P.U.Akinaga, Y., Nakajima, T., Hirao, K., (2001) J. Chem. Phys., 114, pp. 8555-8564Akkerman, H.B., Blom, P.W.M., De Leeuw, D.M., De Boer, B., (2006) Nature, 441, pp. 69-72Akkerman, H.B., Kronemeijer, A.J., Van Hal, P.A., De Leeuw, D.M., Blom, P.W.M., De Boer, B., (2008) Small, 4, pp. 100-104Allara, D.L., (1995) Biosens. Bioelectron., 10, pp. 771-783Bain, C.D., Troughton, E.B., Tao, Y.T., Evall, J., Whitesides, G.M., Nuzzo, R.G., (1989) J. Am. Chem. Soc., 111, pp. 321-335Baralia, G.G., Pallandre, A., Nysten, B., Jonas, A.M., (2006) Nanotechnology, 17, pp. 1160-1165Beardmore, K.M., Kress, J.D., Gronbech-Jensen, N., Bishop, A.R., (1998) Chem. Phys. Lett., 286, pp. 40-45Blöchl, P.E., (1994) Phys. Rev. B, 50, pp. 17953-17979Canchaya, J.G.S., Wang, Y., Alcami, M., Martin, F., Busnengo, H.F., (2010) Phys. Chem. Chem. Phys., 12, pp. 7555-7565Cao, Y., Ge, Q., Dyer, D., Wang, L., (2003) J. Phys. Chem. B, 107, pp. 3803-3807Cometto, F.P., Paredes-Olivera, P., MacAgno, V.A., Patrito, E.M., (2005) J. Phys. Chem. B, 109, pp. 21737-21748Cossaro, A., Mazzarello, R., Rousseau, R., Casalis, L., Verdini, A., Kohlmeyer, A., Floreano, L., Scoles, G., (2008) Science, 321, pp. 943-946Dishner, M.H., Hemminger, J.C., Feher, F.J., (1997) Langmuir, 13, pp. 2318-2322Dubois, L.H., Zegarski, B.R., Nuzzo, R.G., (1993) J. Chem. Phys., 98, pp. 678-688Esplandiu, M.J., Carot, M.L., Cometto, F.P., MacAgno, V.A., Patrito, E.M., (2006) Surf. Sci., 600, pp. 155-172Fenter, P., Eberhardt, A., Eisenberger, P., (1994) Science, 266, pp. 1216-1218Fenter, P., Eisenberger, P., Liang, K.S., (1993) Phys. Rev. Lett., 70, pp. 2447-2450Fischer, D., Curioni, A., Andreoni, W., (2003) Langmuir, 19, pp. 3567-3571Flood, A.H., Stoddart, J.F., Steuerman, D.W., Heath, J.R., (2004) Science, 306, pp. 2055-2056Franzen, S., (2003) Chem. Phys. Lett., 381, pp. 315-321Gottschalck, J., Hammer, B., (2002) J. Chem. Phys., 116, pp. 784-790Grönbeck, H., Curioni, A., Andreoni, W., (2000) J. Am. Chem. Soc., 122, pp. 3839-3842Grönbeck, H., Häkkinen, H., Whetten, R.L., (2008) J. Phys. Chem. C, 112, pp. 15940-15942Hayashi, T., Morikawa, Y., Nozoye, H., (2001) J. Chem. Phys., 114, pp. 7615-7621Hohenberg, P., Kohn, W., (1964) Phys. Rev., 136, p. 864. , BB 871Kautz, N.A., Kandel, S.A., (2009) J. Phys. Chem. C, 113, pp. 19286-19291Kohn, W., Sham, L.J., (1965) Phys. Rev., 140, p. 1133. , AA 1138Kondoh, H., Iwasaki, M., Shimada, T., Amemiya, K., Yokoyama, T., Ohta, T., Shimomura, M., Kono, S., (2003) Phys. Rev. Lett., 90, p. 066102Kresse, G., Furthmüller, J., (1996) Phys. Rev. B, 54, pp. 11169-11186Kresse, G., Joubert, D., (1999) Phys. Rev. B, 59, pp. 1758-1775Li, A.H.-T., Chao, S.D., (2006) J. Chem. Phys., 125, p. 094312Lio, A., Charych, D.H., Salmeron, M., (1997) J. Phys. Chem. B, 101, pp. 3800-3805Love, J.C., Estroff, L.A., Kriebel, J.K., Nuzzo, R.G., Whitesides, G.M., (2005) Chem. Rev., 105, pp. 1103-1170Lüssem, B., Müller-Meskamp, L., Karthäuser, S., Waser, R., (2005) Langmuir, 21, pp. 5256-5258Maksymovych, P., Sorescu, D.C., Yates, J.T., (2006) J. Phys. Chem. B, 110, pp. 21161-21167Maksymovych, P., Sorescu, D.C., Yates Jr., J.T., (2006) Phys. Rev. Lett., 97, p. 146103Mazzarello, R., Cossaro, A., Verdini, A., Rousseau, R., Casalis, L., Danisman, M.F., Floreano, L., Scoles, G., (2007) Phys. Rev. Lett., 98, p. 016102Molina, L.M., Hammer, B., (2002) Chem. Phys. Lett., 360, pp. 264-271Monkhorst, H.J., Pack, J.D., (1976) Phys. Rev. B, 13, pp. 5188-5192Nishi, N., Hobara, D., Yamamoto, M., Kakiuchi, T., (2003) J. Chem. Phys., 118, pp. 1904-1911Nuzzo, R.G., Dubois, L.H., Allara, D.L., (1990) J. Am. Chem. Soc., 112, pp. 558-569Nuzzo, R.G., Korenic, E.M., Dubois, L.H., (1990) J. Chem. Phys., 93, pp. 767-773Nuzzo, R.G., Zegarski, B.R., Dubois, L.H., (1987) J. Am. Chem. Soc., 109, pp. 733-740Paradis, E., Rowntree, P., (2003) J. Electroanal. Chem., 550-551, pp. 175-185Perdew, J.P., Wang, Y., (1992) Phys. Rev. B, 45, pp. 13244-13249Peterlinz, K.A., Georgiadis, R., (1996) Langmuir, 12, pp. 4731-4740Poirier, G., (1997) Langmuir, 13, pp. 2019-2026Poirier, G.E., Pylant, E.D., (1996) Science, 272, pp. 1145-1148Porter, M.D., Bright, T.B., Allara, D.L., Chidsey, C.E.D., (1987) J. Am. Chem. Soc., 109, pp. 3559-3568Pyykkö, P., (2008) Chem. Soc. Rev., 37, pp. 1967-1997Roper, M.G., Skegg, M.P., Fisher, C.J., Lee, J.J., Dhanak, V.R., Woodruff, D.P., Jones, R.G., (2004) Chem. Phys. Lett., 389, pp. 87-91Schreiber, F., (2000) Prog. Surf. Sci., 65, pp. 151-257Schwartz, D.K., (2001) Annu. Rev. Phys. Chem., 52, pp. 107-137Sellers, H., Ulman, A., Shnidman, Y., Eilers, J.E., (1993) J. Am. Chem. Soc., 115, pp. 9389-9401Stranick, S.J., Parikh, A.N., Allara, D.L., Weiss, P.S., (1994) J. Phys. Chem., 98, pp. 11136-11142Strong, L., Whitesides, G.M., (1988) Langmuir, 4, pp. 546-558Terán Arce, F., Vela, M.E., Salvarezza, R.C., Arvia, A.J., (1998) J. Chem. Phys., 109, pp. 5703-5706Terán Arce, F., Vela, M.E., Salvarezza, R.C., Arvia, A.J., (1998) Langmuir, 14, pp. 7203-7212Torrelles, X., Vericat, C., Vela, M.E., Fonticelli, M.H., Millone, M.A.D., Felici, R., Lee, T.-L., Salvarezza, R.C., (2006) J. Phys. Chem. B, 110, pp. 5586-5594Torres, E., Biedermann, P.U., Blumenau, A.T., (2009) Int. J. Quantum Chem., 109, pp. 3466-3472Torres, E., Blumenau, A.T., Biedermann, P.U., (2009) Phys. Rev. B, 79, p. 075440Touzov, I., Gorman, C.B., (1997) J. Phys. Chem. B, 101, pp. 5263-5276Tsuzuki, S., Honda, K., Uchimaru, T., Mikami, M., (2004) J. Phys. Chem. A, 108, pp. 10311-10316Tsuzuki, S., Honda, K., Uchimaru, T., Mikami, M., (2006) J. Chem. Phys., 124, p. 114304Tsuzuki, S., Luthi, H.P., (2001) J. Chem. Phys., 114, pp. 3949-3957Ulman, A., (1996) Chem. Rev., 96, pp. 1533-1554Vargas, M.C., Giannozzi, P., Selloni, A., Scoles, G., (2001) J. Phys. Chem. B, 105, pp. 9509-9513Vericat, C., Vela, M.E., Benitez, G., Carro, P., Salvarezza, R.C., (2010) Chem. Soc. Rev., 39, pp. 1805-1834Vericat, C., Vela, M.E., Benitez, G.A., Gago, J.A.M., Torrelles, X., Salvarezza, R.C., (2006) J. Phys. Condens. Matter, 18, p. 867. , RR 900Voznyy, O., Dubowski, J.J., Yates, J.J.T., Maksymovych, P., (2009) J. Am. Chem. Soc., 131, pp. 12989-12993Selloni, A., (2007) J. Phys. Chem. C, 111, pp. 12149-12151Whitesides, G.M., Mathias, J.P., Seto, C.T., (1991) Science, 254, pp. 1312-1319Widrig, C.A., Alves, C.A., Porter, M.D., (1991) J. Am. Chem. Soc., 113, pp. 2805-2810Yourdshahyan, Y., Rappe, A.M., (2002) J. Chem. Phys., 117, pp. 825-833Yu, M., Bovet, N., Satterley, C.J., Bengiõ, S., Lovelock, K.R.J., Milligan, P.K., Jones, R.G., Dhanak, V., (2006) Phys. Rev. Lett., 97, p. 166102http://purl.org/coar/resource_type/c_6501THUMBNAILMiniProdInv.pngMiniProdInv.pngimage/png23941https://repositorio.utb.edu.co/bitstream/20.500.12585/9113/1/MiniProdInv.png0cb0f101a8d16897fb46fc914d3d7043MD5120.500.12585/9113oai:repositorio.utb.edu.co:20.500.12585/91132021-02-02 14:08:00.375Repositorio Institucional UTBrepositorioutb@utb.edu.co |