Classical Molecular Dynamics Simulation ofMetal Electrodes-Electrolyte Interface

Abstract

電極電解液界面ではバルクの溶液とは大きく異なる特異な溶媒構造のもとで多彩かつ重要な反応が進行する．古典動力学シミュレーションは反応場としての電極電解液界面に対する微視的な理解を得ることが出来る有効なアプローチの一つである．本稿では，金属電極電解質水溶液系の古典動力学シミュレーションを行うにあたり注意すべき三点: 相互作用ポテンシャルの選択，電極の分極と定電位条件の記述，長距離静電相互作用の評価 について述べる．

Figures

Figure 1.

Electrostatic potenial profile obtained from Gouy-Chapman-Stern model for an electrode-electrolyte interface.

Figure 2.

Electrostatic potenial profile obtained from an all atom simulation.

Figure 3.

Potential of mean force profiles for a sodium cation approaching a negatively charged Pt electrode in aqueous solution calculated from trajectories ranging from 10 ns to 500 ns. The horizontal axis shows the distance from the negatively charged electrode.

Figure 4.

Number density profiles along the direction normal to the surfaces of the Pt metal electrodes. The system is composed of a positively charged Pt electrode (left electrode), a negatively charged Pt electrode (right electrode), and 1 M K₃Fe(CN)₆ aqueous solution, with 2 V voltage applied between the two electrodes. The profiles for atoms Fe in Fe(CN)₆^3-, K, O in water molecules are shown.

Figure 5.

Poisson potential profile along the direction normal to the surfaces of the Pt metal electrodes calculated for the same system as described in Figure 4.

Figure 6.

 A slab model for studying an electrode-electrolyte interface. This model consists of two electrode layers (gold spheres), solvent (red and white spheres), and vacuum layers, all of which are contained in the primary cell (its boundaries are indicated with black lines).

References

• [1]   Allen J Bard and Larry R Faulkner, Electrochemical methods: fundamentals and applications. New York: Wiley, 2 edition, 2001.
• [2]   Y. Matsumi, H. Nakano, H. Sato, Chem. Phys. Lett., 681, 80 (2017).
• [3]   H. Nakano, Y. Matsumi, H. Sato, in press.
• [4]   A. Hodgson, S. Haq, Surf. Sci. Rep., 64, 381 (2009).
• [5]   S. Sakong, K. Forster-Tonigold, A. Groß, J. Chem. Phys., 144, 194701 (2016).
• [6]   S. Sakong, M. Naderian, K. Mathew, R. G. Hennig, A. Groß, J. Chem. Phys., 142, 234107 (2015).
• [7]   J. Le, A. Cuesta, J. Cheng, J. Electroanal. Chem., 819, 87 (2018).
• [8]   A. Michaelides, V. A. Ranea, P. L. de Andres, D. A. King, Phys. Rev. Lett., 90, 216102 (2003).
• [9]   B. Temelso, K. A. Archer, G. C. Shields, J. Phys. Chem. A, 115, 12034 (2011).
• [10]   B. Hammer, L. B. Hansen, J. K. Nørskov, Phys. Rev. B, 59, 7413 (1999).
• [11]   S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys., 132, 154104 (2010).
• [12]   J. I. Siepmann, M. Sprik, J. Chem. Phys., 102, 511 (1995).
• [13]   A. P. Willard, S. K. Reed, P. A. Madden, D. Chandler, Faraday Discuss., 141, 423 (2009).
• [14]   D. T. Limmer, A. P. Willard, P. A. Madden, D. Chandler, J. Phys. Chem. C, 119, 24016 (2015).
• [15]   S. N. Steinmann, R. Ferreira De Morais, A. W. Götz, P. Fleurat-Lessard, M. Iannuzzi, P. Sautet, C. Michel, J. Chem. Theory Comput., 14, 3238 (2018).
• [16]   K. Raghavan, K. Foster, K. Motakabbir, M. Berkowitz, J. Chem. Phys., 94, 2110 (1991).
• [17]   K.-Y. Yeh, M. J. Janik, J. K. Maranas, Electrochim. Acta, 101, 308 (2013).
• [18]   N. Onofrio, A. Strachan, J. Chem. Phys., 143, 054109 (2015).
• [19]   S. K. Natarajan, J. Behler, Phys. Chem. Chem. Phys., 18, 28704 (2016).
• [20]   A. A. Lee, S. Perkin, J. Phys. Chem. Lett., 7, 2753 (2016).
• [21]   J. Vatamanu, D. Bedrov, O. Borodin, Mol. Simul., 43, 838 (2017).
• [22]   K. Takae, A. Onuki, J. Phys. Chem. B, 119, 9377 (2015).
• [23]   A. P. dos Santos, M. Girotto, Y. Levin, J. Chem. Phys., 147, 184105 (2017).
• [24]   M. K. Petersen, R. Kumar, H. S. White, G. A. Voth, J. Phys. Chem. C, 116, 4903 (2012).
• [25]   A. K. Rappe, W. A. Goddard, J. Phys. Chem., 95, 3358 (1991).
• [26]   S. W. Rick, S. J. Stuart, B. J. Berne, J. Chem. Phys., 101, 6141 (1994).
• [27]   C. G. Guymon, R. L. Rowley, J. N. Harb, D. R. Wheeler, Condens. Matter Phys., 8, 335 (2005).
• [28]   T. Liang, A. C. Antony, S. A. Akhade, M. J. Janik, S. B. Sinnott, J. Phys. Chem. A, 122, 631 (2018).
• [29]   S. K. Reed, O. J. Lanning, P. A. Madden, J. Chem. Phys., 126, 084704 (2007).
• [30]   S. K. Reed, P. A. Madden, A. Papadopoulos, J. Chem. Phys., 128, 124701 (2008).
• [31]   A. Arnold, J. de Joannis, C. Holm, J. Chem. Phys., 117, 2496 (2002).
• [32]   S. Tyagi, A. Arnold, C. Holm, J. Chem. Phys., 129, 204102 (2008).
• [33]   A. Arnold, C. Holm, Comput. Phys. Commun., 148, 327 (2002).
• [34]   S. W. de Leeuw, J. W. Perram, E. R. Smith, Proc.- Royal Soc.A, Math. Phys. Eng. Sci., 373, 27 (1980).
• [35]   E. R. Smith, J. S. Rowlinson, Proc.- Royal Soc. A, Math. Phys. Eng. Sci., 375, 475 (1981). DOI:10.1098/rspa.1981.0064
• [36]   H. D. Herce, A. E. Garcia, T. Darden, J. Chem. Phys., 126, 124106 (2007).
• [37]   M. Mazars, Phys. Rep., 500, 43 (2011).
• [38]   A. P. dos Santos, M. Girotto, Y. Levin, J. Chem. Phys., 144, 144103 (2016).
• [39]   I. -C. Yeh, M. L. Berkowitz, J. Chem. Phys., 111, 3155 (1999).