Abstract
I describe the direct observation of H-bond exchange reaction within a water dimer isolated on a Cu(110) surface in this chapter. A water dimer consisted of H-bond donor and acceptor molecule can be produced by the association of water monomers. The STM image of a dimer is characterized by an incessant fluctuation between two states. Combined with DFT calculations it is found that the fluctuation corresponds to the H-bond donor–acceptor interchange where the role of each molecule is exchanged within a dimer. To elucidate the mechanism the interchange rate is investigated using the time-resolved measurement of STM. The voltage and current dependence of the rate unveil the interchange is not induced by STM, thus inherent in a dimer, at low bias voltages (V s < 40 mV). Furthermore, it is found that the rate of (H2O)2 is ~60 times larger than that of (D2O)2 in the low voltage region, indicating that the interchange process includes quantum tunneling. The voltage dependence also reveals the interchange rate is increased by the excitation of the intermolecular vibration mode of a dimer through the vibrationally assisted tunneling process.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Notes
- 1.
The calculations were based on the density functional theory using a planewave, pseudopotential code STATE [Y. Morikawa, Phys. Rev. B 51, 14802 (1995).]. Five-layer Cu slabs with surface were used in the calculation and water dimers arrayed in a 2 × 3 surface unit cell and a k-space sampling at 16 points. Adsorbates and two top Cu layers were relaxed.
- 2.
The STM simulation was conducted based on the Tersoff-Hamann approach [J. Tersoff and D. R. Hamann, Phys. Rev. Lett. 50, 1998 (1983).] with a 3 × 4 unit cell and finer 64 k points. In the calculation of the simulation images, the sample bias voltage and the tip height were set at 24 mV and 0.5 nm, respectively. We confirmed that the qualitative features were not affected by the tip height. The molecular graphics were produced by the XCRYSDEN graphical package [A. Kokalj, Comput. Mater. Sci. 28, 155 (2003). Code available from http://www.xcrysden.org/]
.
References
T.R. Dyke, J. Chem. Phys. 66, 492 (1977)
T.R. Dyke, K.M. Mack, J.S. Muenter, J. Chem. Phys. 66, 498 (1977)
J.A. Odutola, T.R. Dyke, J. Chem. Phys. 72, 5062 (1980)
J.A. Odutola, T.A. Hu, D. Prinslow, S.E. O’dell, T.R. Dyke, J. Chem. Phys. 88, 5352 (1988)
R.S. Fellers, C. Leforestier, L.B. Braly, M.G. Brown, R.J. Saykally, Science 284, 945 (1999)
K.L. Busarow, R.C. Cohen, Geoffrey A. Blake, K.B. Laughlin, Y.T. Lee, and R.J. Saykally. J. Chem. Phys. 90, 3937 (1989)
G.T. Fraser, Int. Rev. Phys. Chem. 10, 189 (1991)
E. Zwart, J.J. ter Meulen, W. Leo Meerts, L.H. Coudert, J. Mol. Spectrosc. 147, 27 (1991)
B.J. Smith, D.J. Swanton, J.A. Pople, H.F. Schaefer, L. Radom, J. Chem. Phys. 92, 1240 (1990)
N. Pugliano, J.D. Cruzan, J.G. Loeser, R.J. Saykally, J. Chem. Phys. 98, 6600 (1993)
T. Mitsui, M.K. Rose, E. Fomin, D.F. Ogletree, M. Salmeron, Science 297, 1850 (2002)
V.A. Ranea, A. Michaelides, R. Ramírez, P.L. de Andres, J.A. Vergés, D.A. King, Phys. Rev. Lett. 92, 136104 (2004)
S. Meng, E.G. Wang, S. Gao, Phys. Rev. B 69, 195404 (2004)
A. Michaelides, K. Morgenstern, Nature Mat. 6, 597 (2007)
R.L. Redington, J. Chem. Phys. 113, 2319 (2000)
K. Motobayashi, C. Matsumoto, Y. Kim, M. Kawai, Surf. Sci. 602, 3136 (2008)
A. Mugarza, T. Shimizu, D.F. Ogletree, M. Salmeron, Surf. Sci. 603, 2030 (2009)
L. Arnadottir, E.M. Stuve, H. Jonsson, Surf. Sci. 604, 1978 (2010)
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
Copyright information
© 2012 Springer Japan
About this chapter
Cite this chapter
Kumagai, T. (2012). Water Dimer: Direct Observation of Hydrogen-Bond Exchange. In: Visualization of Hydrogen-Bond Dynamics. Springer Theses, vol 125. Springer, Tokyo. https://doi.org/10.1007/978-4-431-54156-1_5
Download citation
DOI: https://doi.org/10.1007/978-4-431-54156-1_5
Published:
Publisher Name: Springer, Tokyo
Print ISBN: 978-4-431-54155-4
Online ISBN: 978-4-431-54156-1
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)