Static and time-resolved X-ray absorption spectroscopy (XAS) is used to probe the solvent shell structure around iodide and iodine. In particular, we characterize the changes observed upon electron abstraction of aqueous iodide, which reflects the transition from hydrophilic to hydrophobic solvation after impulsive electron abstraction from iodide. The static spectrum of aqueous iodide, which is analyzed using quantum mechanical/molecular mechanics (QM/MM) molecular dynamics (MD) simulations, indicates that the hydrogens of the closest water molecules point toward the iodide, as expected for hydrophilic solvation. In addition, these simulations demonstrate a small anisotropy in the solvent shell. Following electron abstraction, most of the water molecules move away from iodine, while one comes closer to form a complex with it that survives for 3–4 ps. This lifetime is governed by the reorganization of the main solvation shell, basically the time it takes for the water molecules to reform a hydrogen bond network in the hydrophobic solvation shell.
Conference
International Conference on Solution Chemistry (ICSC-32), International Conference on Solution Chemistry, ICSC, Solution Chemistry, 32nd, La Grande Motte, France, 2011-08-28–2011-09-02
References
1 10.1021/cr000692+, L. R. Pratt, A. Pohorille. Chem. Rev.102, 2671 (2002).Search in Google Scholar PubMed
2 10.1146/annurev.biophys.34.040204.144517, K. A. Dill, T. M. Truskett, V. Vlachy, B. Hribar-Lee. Annu. Rev. Biophys. Biomol. Struct.34, 173 (2005).Search in Google Scholar PubMed
3 10.1073/pnas.0700176104, G. Galli. Proc. Natl. Acad. Sci. USA104, 2557 (2007).Search in Google Scholar PubMed PubMed Central
4 10.1146/annurev.physchem.58.032806.104445, B. J. Berne, J. D. Weeks, R. Zhou. Annu. Rev. Phys. Chem.60, 85 (2009).Search in Google Scholar PubMed PubMed Central
5 10.1021/jp980642x, S. Koneshan, J. C. Rasaiah, R. M. Lynden-Bell, S. H. Lee. J. Phys. Chem. B102, 4193 (1998).Search in Google Scholar
6 10.1021/j150670a013, R. M. Lynden-Bell, W. A. Steele. J. Phys. Chem.88, 6514 (1984).Search in Google Scholar
7 10.1063/1.468323, S. L. Lee, J. C. Rashaiah. J. Chem. Phys.101, 6964 (1994).Search in Google Scholar
8 10.1021/jp953050c, S. L. Lee, J. C. Rashaiah. J. Phys. Chem.100, 1420 (1996).Search in Google Scholar
9 10.1146/annurev.physchem.012809.103353, C. Bressler, M. Chergui. Annu. Rev. Phys. Chem.61, 263 (2010).Search in Google Scholar PubMed
10 10.1107/S010876730904968X, M. Chergui. Acta Crystallogr., Sect. A66, 229 (2010).Search in Google Scholar PubMed
11 10.1524/zkri.2008.0030, C. Bressler, R. Abela, M. Chergui. Z. Kristallogr.223, 308 (2008).Search in Google Scholar
12 10.1126/science.1165733, C. Bressler, C. Milne, V. T. Pham, A. El Nahhas, R. M. van der Veen, W. Gawelda, S. L. Johnson, P. Beaud, D. Grolimund, M. Kaiser, C. N. Borca, G. Ingold, R. Abela, M. Chergui. Science323, 489 (2009).Search in Google Scholar PubMed
13 10.1063/1.1633003, M. Saes, F. van Mourik, W. Gawelda, M. Kaiser, M. Chergui, C. Bressler, D. Grolimund, R. Abela, T. E. Glover, P. Heimann, R. W. Schoenlein, S. L. Johnson, A. M. Lindenberg, R. W. Falcone. Rev. Sci. Instrum.75, 24 (2004).Search in Google Scholar
14 10.1016/j.chemphys.2010.03.023, V. T. Pham, I. Tavernelli, C. J. Milne, R. M. van der Veen, P. D’Angelo, C. Bressler, M. Chergui. Chem. Phys.371, 24 (2010).Search in Google Scholar
15 10.1021/ja203882y, V. T. Pham, T. J. Penfold, R. M. van der Veen, F. Lima, A. El Nahhas, S. L. Johnson, P. Beaud, R. Abela, C. Bressler, I. Tavernelli, C. J. Milne, M. Chergui. J. Am. Chem. Soc.133, 12740 (2011).Search in Google Scholar PubMed
16 10.1103/PhysRevLett.99.174801, P. Beaud, S. Johnson, A. Streun, R. Abela, D. Abramsohn, D. Grolimund, F. Krasniqi, T. Schmidt, V. Schlott, G. Ingold. Phys. Rev. Lett.99, 174801 (2007).Search in Google Scholar PubMed
17 10.1021/jp0143138, A. Laio, J. VandeVondele, U. Rothlisberger. J. Phys. Chem. B106, 7300 (2002).Search in Google Scholar
18 10.1063/1.1462041, A. Laio, J. VandeVondele, U. Rothlisberger. J. Chem. Phys.116, 6941 (2002).Search in Google Scholar
19 U. Rothlisberger, P. Carloni. Lect. Notes Phys.704, 437 (2006).Search in Google Scholar
20 10.2533/chimia.2011.667, E. Brunk, N. Ashari, P. Athri, P. Campomanes, B. F. E. Curchod, P. Diamantis, M. Doemer, J. Garrec, A. Laktionov, M. Micciarelli, M. Neri, G. Palermo, T. J. Penfold, S. Vanni, I. Tavernelli, U. Rothlisberger. Chimia65, 667 (2011).Search in Google Scholar PubMed
21 T. J. Penfold, I. Tavernelli, M. Doemer, U. Rothlisberger, M. Chergui. Chem. Phys. Submitted for publication.Search in Google Scholar
22 10.1246/bcsj.76.1735, H. Tanida, K. Kato, I. Watanabe. Bull. Chem. Soc. Jpn.76, 1735 (2003).Search in Google Scholar
23 10.1021/jp806782r, C. J. Wick, S. S. Xantheas. J. Phys. Chem. B113, 4141 (2009).Search in Google Scholar PubMed
24 10.1021/ja068466q, V. T. Pham, W. Gawelda, Y. Zaushitsyn, M. Kaiser, D. Grolimund, S. L. Johnson, R. Abela, C. Bressler, M. Chergui. J. Am. Chem. Soc.129, 1530 (2007).Search in Google Scholar PubMed
25 10.1021/jp964097g, M. D. Sevilla, S. Summerfield, I. Eliezer, J. Rak, M. C. R. Symons. J. Phys. Chem. A101, 2910 (1997).Search in Google Scholar
26 10.1063/1.2827456, C. G. Elles, I. A. Shkrob, R. A. Crowell, D. A. Arms, E. C. Landahl. J. Chem. Phys.128, 061102 (2008).Search in Google Scholar PubMed
27 10.1002/qua.560260111, I. Mayer. Int. J. Quantum Chem.26, 151 (1984).Search in Google Scholar
28 10.1021/jp9820830, F. M. Bickelhaupt, A. Diefenbach, S. P. de Visser, L. J. de Koning, N. M. M. Nibber-ing. J. Phys. Chem. A102, 9549 (1998).Search in Google Scholar
© 2013 Walter de Gruyter GmbH, Berlin/Boston
