Abstract
The structure and energetic properties of self-assembled monolayers (SAMs) of alkanethiol derivatives (simple alkanethiols, mercaptoalkanoic acids and aminoalkanethiols with different chain length) adsorbed on the metallic Au(111) surface are investigated through periodic DFT calculations. To sort out the effect of van der Waals (vdW) interactions on the DFT calculations, the results of the standard GGA–PBE functional are compared with those obtained with approaches including the vdW interactions such as those incorporating the Grimme’s (GGA–PBE-D2) and the Tkatchenko–Scheffler’s (GGA–PBE-TS) schemes, as well as with the optB86b-vdW density functional. The most significant difference between the two sets of results appears for the adsorption energies per thiol molecules: The standard functional predicts energy values 30–40 % lower than those obtained when the van der Waals interactions are taken into account. This is certainly due to a better description of the lateral interactions between the chains of the thiols when including the van der Waals effects. Differences are also found between the adsorption energies predicted by density functionals taking into account the vdW corrections, with values increasing in the order GGA–PBE-D2 < GGA–PBE-TS < optB86b-vdW. Furthermore, the functionals considering dispersion interactions favor much more tilted orientations of the SAMs over the surface with respect to those found using the standard GGA functional (the SAMs’ tilt angles increase from 17°–24° to 37°–46°), being the former in closer agreement with available experimental data. In contrast, the SAMs’ precession angle and monolayer thickness are less affected by the type of DFT exchange–correlation functional employed. In the case of low surface coverage, the chains of the thiols adopt more tilted configurations and tend to lay side-down onto the surface.
Similar content being viewed by others
References
Domínguez CSH, Quintana C, Vicente J, Hernández P, Hernández L (2008) Talanta 74:1014–1019
Dong X-D, Lu J, Cha C (1995) Bioelectrochem Bioenerg 36:73–76
Guo C, Boullanger P, Jiang L, Liu T (2008) Colloid Surf B 62:146–150
Kondo M, Nakamura Y, Fujii K, Nagata M, Suemori Y, Dewa T, Iida K, Gardiner AT, Cogdell RJ, Nango M (2007) Biomacromolecules 8:2457–2463
Crivillers N, Mas-Torrent M, Vidal-Gancedo J, Veciana J, Rovira C (2008) J Am Chem Soc 130:5499–5506
Pattanaik G, Shao W, Swami N, Zangari G (2009) Langmuir 25:5031–5038
Li F, Tang L, Zhou W, Guo Q (2009) J Phys Chem C 113:17899–17903
Palyvoda O, Bordenyuk AN, Yatawara AK, McCullen E, Chen C-C, Benderskii AV, Auner GW (2008) Langmuir 24:4097–4106
Jacobsen V, Zhu T, Knoll W, Kreiter M (2005) Eur J Inorg Chem 2005:3683–3690
Campiña JM, Martins A, Silva F (2009) Electrochem Acta 55:90–103
Lim I-IS, Ip W, Crew E, Njoki PN, Mott D, Zhong C-J, Pan Y, Zhou S (2007) Langmuir 23:826–833
Taylor AD, Ladd J, Etheridge S, Deeds J, Hall S, Jiang S (2008) Sens Actuator B 130:120–128
Waring C, Bagot PAJ, Räisänen MT, Costen ML, McKendrick KG (2009) J Phys Chem A 113:4320–4329
Dubois C, Stellacci F (2008) J Phys Chem C 112:7431–7435
Dubois LH, Zegarski BR, Nuzzo RG (1993) J Chem Phys 98:678–688
Laiho T, Leiro JA (2008) Surf Interface Anal 40:51–59
Müller-Meskamp L, Karthäuser S, Waser R, Homberger M, Simon U (2008) Langmuir 24:4577–4580
Oh SY, Chung CM, Kim DH, Lee SG (2008) Colloid Surf A 313–314:600–603
Okabayashi N, Konda Y, Komeda T (2008) Phys Rev Lett 100:217801
Béthencourt MI, Srisombat L-O, Chinwangso P, Lee TR (2009) Langmuir 25:1265–1271
Sharma M, Komiyama M, Engstrom JR (2008) Langmuir 24:9937–9940
Silien C, Buck M, Goretzki G, Lahaye D, Champness NR, Weidner T, Zharnikov M (2009) Langmuir 25:959–967
Staub R, Toerker M, Fritz T, Schmitz-Hübsch T, Sellam F, Leo K (2000) Surf Sci 445:368–379
Ge Y, Weidner T, Ahn H, Whitten JE, Zharnikov M (2009) J Phys Chem C 113:4575–4583
Subramanian S, Sampath S (2007) Anal Bioanal Chem 388:135–145
Lamb BM, Barrett DG, Westcott NP, Yousaf MN (2008) Langmuir 24:8885–8889
Pace G, Petitjean A, Lalloz-Vogel M-N, Harrowfield J, Lehn J-M, Samorì P (2008) Angew Chem Int Ed 47:2484–2488
Phong PH, Tomono H, Nishi N, Yamamoto M, Kakiuchi T (2008) Electrochim Acta 53:4900–4906
Hayashi T, Wakamatsu K, Ito E, Hara M (2009) J Phys Chem C 113:18795–18799
Srisombat L-O, Zhang S, Lee TR (2010) Langmuir 26:41–46
Nadler R, Sánchez-de-Armas R, Sanz JF (2011) Comput Theoretical Chem 975:116–121
Hattori S, Kano S, Azuma Y, Majima Y (2010) J Phys Chem C 114:8120–8125
Cossaro A, Mazzarello R, Rousseau R, Casalis L, Verdini A, Kohlmeyer A, Floreano L, Scandolo S, Morgante A, Klein ML, Scoles G (2008) Science 321:943–946
Tielens F, Santos E (2010) J Phys Chem C 114:9444–9452
Kankate L, Turchanin A, Gölzhäuser A (2009) Langmuir 25:10435–10438
Sellers H, Ulman A, Shnidman Y, Eilers JE (1993) J Am Chem Soc 115:9389–9401
Cortés E, Rubert AA, Benitez G, Carro P, Vela ME, Salvarezza RC (2009) Langmuir 25:5661–5666
Desikan R, Armel S, Meyer HM III, Thundat T (2007) Nanotechnology 18:424028
Torres E, Blumenau AT, Biedermann PU (2011) Chem Phys Chem 12:999–1009
Fenter P, Eberhardt A, Liang KS, Eisenberger P (1997) J Chem Phys 106:1600–1608
Fenter P, Eisenberger P, Liang KS (1993) Phys Rev Lett 70:2447–2450
Li T-W, Chao I, Tao Y-T (1998) J Phys Chem B 102:2935–2946
Sung I-H, Kim D-E (2004) Tribol Lett 17:835–844
Tsai M-Y, Lin J-C (2001) J Colloid Interface Sci 238:259–266
Woodward JT, Walker ML, Meuse CW, Vanderah DJ, Poirier GE, Plant AL (2000) Langmuir 16:5347–5353
Noh J, Hara M (2011) RIKEN Rev: focused on nanotechnology in RIKEN II 38:49–51
Terrill RH, Tanzer TA, Bohn PW (1998) Langmuir 14:845–854
Kautz NA, Kandel SA (2009) J Phys Chem C 113:19286–19291
Kautz NA, Kandel SA (2008) J Am Chem Soc 130:6908–6909
Torres E, Biedermann PU, Blumenau AT (2009) Int J Quantum Chem 109:3466–3472
Wang J-G, Selloni A (2009) J Phys Chem C 113:8895–8900
Maksymovych P, Sorescu DC, Yates JT (2006) Phys Rev Lett 97:146103 (1–4)
Rosu DM, Jones JC, Hsu JWP, Kavanagh KL, Tsankov D, Schade U, Esser N, Hinrichs K (2009) Langmuir 25:919–923
Mendoza SM, Arfaoui I, Zanarini S, Paolucci F, Rudolf P (2007) Langmuir 23:582–588
Chuang W-H, Lin J-C (2007) J Biomed Mater Res A 82:820–830
Iqbal P, Critchley K, Attwood D, Tunnicliffe D, Evans SD, Preece JA (2008) Langmuir 24:13969–13976
Lee S-H, Lin W-C, Kuo C-H, Karakachian M, Lin Y-C, Yu B-Y, Shyue J-J (2010) J Phys Chem C 114:10512–10519
Fadda AA, Abdel-Latif E, El-Mekawy RE (2009) Eur J Med Chem 44:1250–1256
Ge Y, Whitten JE (2008) J Phys Chem C 112:1174–1182
Sändig N, Biscarini F, Zerbetto F (2008) J Phys Chem C 112:19516–19520
Harpham MR, Süzer O, Ma C-Q, Bäuerle P, Goodson T III (2009) J Am Chem Soc 131:973–979
Tang ML, Mannsfeld SCB, Sun Y-S, Becerril HA, Bao Z (2009) J Am Chem Soc 131:882–883
Nogues C, Lang P, Desbat B, Buffeteau T, Leiserowitz L (2008) Langmuir 24:8458–8464
Duffy DM, Harding JH (2005) Langmuir 21:3850–3857
Alkis S, Jiang P, Wang L-L, Roitberg AE, Cheng H-P, Krause JL (2007) J Phys Chem C 111:14743–14752
Bhatia R, Garrison BJ (1997) Langmuir 13:765–769
Bhatia R, Garrison BJ (1997) Langmuir 13:4038–4043
Dirama TE, Johnson JA (2007) Langmuir 23:12208–12216
Ghorai PK, Glotzer SC (2007) J Phys Chem C 111:15857–15862
Mar W, Klein ML (1994) Langmuir 10:188–196
Jia J, Huang YD, Long J, He JM, Zhang HX (2009) App Surf Sci 255:6451–6459
Carro P, Creus AH, Muñoz A, Salvarezza RC (2010) Langmuir 26:9589–9595
Lee H-H, Ružele Ž, Malysheva L, Onipko A, Gutés A, Björefors F, Valiokas R, Liedberg B (2009) Langmuir 25:13959–13971
Grönbeck H, Häkkinen H, Whetten RL (2008) J Phys Chem C 112:15940–15942
Grönbeck H (2010) J Phys Chem C 114:15973–15978
Leng J-C, Lin L-L, Song X-N, Li Z-L, Wang C-K (2009) J Phys Chem C 113:18353–18357
Majumder C (2008) Langmuir 24:10838–10842
Fletcher MC, Vivoni A, Moore MM, Lui J, Caldwell J, Prokes SM, Glembocki O, Hosten CM (2008) Surf Sci 602:1614–1621
Rajaraman G, Caneschi A, Gatteschi D, Totti F (2010) J Mater Chem 20:10747–10754
Alexiadis O, Daoulas KC, Mavrantzas VG (2008) J Phys Chem B 112:1198–1211
Szefczyk B, Franco R, Gomes JANF, Cordeiro MNDS (2010) J Mol Struct: Theochem 946:83–87
Campiña JM, Martins A, Silva F (2007) J Phys Chem C 111:5351–5362
Battaglini N, Repain V, Lang P, Horowitz G, Rousset S (2008) Langmuir 24:2042–2050
Epple M, Bittner AM, Kuhnke K, Kern K, Zheng W-Q, Tadjeddine A (2002) Langmuir 18:773–784
Kresse G, Hafner J (1993) Phys Rev B 47:558–561
Kresse G, Furthmüller J (1996) Comput Mater Sci 6:15–50
Kresse G, Furthmüller J (1996) Phys Rev B 54:11169–11186
Perdew JP, Burke K, Ernzerhof M (1996) Phys Rev Lett 67:3865–3868
Grimme S (2006) J Comput Chem 27:1787–1799
Tkatchenko A, Scheffler M (2009) Phys Rev Lett 102:073005
Klimeš J, Bowler DR, Michaelides A (2010) J Phys: Cond Matt 22:022201
Andersson MP (2013) J Theor Chem 2013:327839
Prates Ramalho JP, Gomes JRB, Illas F (2013) RSC Adv 3:13085–13100
Blöchl PE (1994) Phys Rev B 50:17953–17979
Kresse G, Joubert D (1999) Phys Rev B 59:1758–1775
Fajín JLC, Cordeiro MNDS, Gomes JRB (2011) Chem Comm 47:8403–8405
Fajín JLC, Gomes JRB, Cordeiro MNDS (2013) Langmuir 29:8856–8864
Fajín JLC, Cordeiro MNDS, Gomes JRB (2007) J Phys Chem C 111:17311–17321
Rai B, Sathish P, Malhotra CP, Pradip, Ayappa KG (2004) Langmuir 20:3138–3144
Fertitta E, Voloshina E, Paulus B (2014) J Comput Chem 35:204–213
Acknowledgments
Thanks are due to Fundação para a Ciência e Tecnologia (FCT), Lisbon, Portugal, and to FEDER for financial support to REQUIMTE (projects Pest-C/EQB/LA0006/2013 and NORTE-07-0124-FEDER-000067-NANOCHEMISTRY) and to CICECO (project Pest-C/CTM/LA0011/2013) and for Programa Investigador FCT. This work is supported also by FCT through project PTDC/QUI–QUI/117439/2010 (FCOMP-01-0124-FEDER-020977) co-financed by Programa COMPETE. JLCF acknowledges FCT for the grant SFRH/BPD/64566/2009 co-financed by the Programa Operacional Potencial Humano (POPH)/Fundo Social Europeu (FSE); Quadro de Referência Estratégico Nacional 2009–2013 do Governo da República Portuguesa.
Author information
Authors and Affiliations
Corresponding authors
Additional information
Published as part of the special collection of articles derived from the 9th Congress on Electronic Structure: Principles and Applications (ESPA 2014).
Rights and permissions
About this article
Cite this article
Fajín, J.L.C., Teixeira, F., Gomes, J.R.B. et al. Effect of van der Waals interactions in the DFT description of self-assembled monolayers of thiols on gold. Theor Chem Acc 134, 67 (2015). https://doi.org/10.1007/s00214-015-1666-y
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00214-015-1666-y