Using cluster studies to approach the electronic structure of bulk water: Reassessing the vacuum level, conduction band edge, and band gap of water

Journal of Chemical Physics

Volumn 107, Issue 16, 1997, Pages 6023-6031

  Coe, James V ^a   Earhart, Alan D ^a   Cohen, Michael H ^a   Hoffman, Gerald J ^b,d   Sarkas, Harry W ^c   Bowen, Kit H ^c  

^a OHIO STATE UNIVERSITY   (United States)

^b POMONA COLLEGE   (United States)

^c JOHNS HOPKINS UNIVERSITY   (United States)

^d The College of New Jersey   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ELECTRONS; ENERGY GAP; FREE RADICALS; HYDROGEN INORGANIC COMPOUNDS; PHOTOEMISSION; POLARIZATION; SOLVENTS; WATER;

ANIONIC DEFECT; CONDUCTION BAND EDGE; ENERGY DIAGRAM; HYDRATED ELECTRON CLUSTER; PHOTOEMISSION THRESHOLD; SOLVATION ENERGY; VACUUM LEVEL;

ELECTRONIC STRUCTURE;

EID: 0031244734     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.474271     Document Type: Article

References (75)

1. S. T. Arnold, J. V. Coe, J. G. Eaton, C. B. Freidhoff, L. Kidder, G. H. Lee, M. R. Manaa, K. M. McHugh, D. Patel-Misra, H. W. Sarkas, J. T. Snodgrass, and K. H. Bowen, in The Chemical Physics of Atomic and Molecular Clusters, edited by G. Scoles (North-Holland, Amsterdam, 1990).
2. G. Markovich, R. Giniger, M. Levin, and O. Cheshnovsky, J. Chem. Phys. 95, 9416 (1991).
3. K. Liu, J. D. Cruzan, and R. J. Saykally, Science 271, 929 (1996).
4. M. Ahmed, C. J. Apps, C. Hughes, and J. C. Whitehead, J. Phys. Chem. 98, 12 530 (1994).
5. T. Schindler, C. Berg, G. Niedner-Schatteburg, and V. E. Bondybey, Chem. Phys. Lett. 250, 301 (1996).
6. F. Williams, S. P. Varma, and S. Hillenius, J. Chem. Phys. 64, 1549 (1976).
7. M. Szklarczyk, R. C. Kainthla, J. O'M. Bockris, J. Electrochem. Soc. 136, 2512 (1989); see Fig. 17 after T. Watanabe and H. Gerischer, J. Electroanal. Chem. 122, 73 (1981).
8. M. Szklarczyk, R. C. Kainthla, J. O'M. Bockris, J. Electrochem. Soc. 136, 2512 (1989); see Fig. 17 after T. Watanabe and H. Gerischer, J. Electroanal. Chem. 122, 73 (1981).
9. T. Goulet, A. Bernas, C. Ferradini, and J.-P. Jay-Gerin, Chem. Phys. Lett. 170, 492 (1990).
10. J. V. Coe, G. H. Lee, J. G. Eaton, S. T. Arnold, H. W. Sarkas, K. H. Bowen, C. Ludewigt, H. Haberland, and D. R. Worsnop, J. Chem. Phys. 92, 3980 (1990).
11. G. Markovich, S. Pollack, R. Giniger, and O. Cheshnovsky, J. Chem. Phys. 101, 9344 (1994).
12. J. V. Coe, J. Phys. Chem. A 101, 2055 (1997).
13. R. C. Weast, Ed., CRC Handbook of Chemistry and Physics, 66th ed. (CRC, Boca Raton, 1985).
14. J. V. Coe, Chem. Phys. Lett. 229, 161 (1994).
15. M. D. Tissandier, K. A. Cowen, W. Y. Feng, E. Gundlach, M. H. Cohen, A. D. Earhart, and J. V. Coe, J. Phys. Chem. (submitted).
16. P. Delahay and K. Von Burg, Chem. Phys. Lett. 83, 250 (1981).
17. P. Delahay, Acc. Chem. Res. 15, 40 (1982).
18. I. Watanabe, J. B. Flanagan, and P. Delahay, J. Chem. Phys. 73, 2057 (1980).
19. P. Delahay and A. Dziedzic, J. Chem. Phys. 80, 5381 (1984).
20. P. Delahay and A. Dziedzic, Chem. Phys. Lett. 108, 169 (1984).
21. M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Peterson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, and J. A. Pople, GAUSSIAN 94, Revision B.2, Gaussian Inc., Pittsburgh, PA, 1995; this small basis set is the biggest available in GAUSSIAN 94W which goes up to iodine.
22. D. Grand, A. Bernas, and E. Amouyal, Chem. Phys. 44, 73 (1979).
23. R. E. Ballard, Chem. Phys. Lett. 16, 300 (1972).
24. M. Knapp, O. Echt, D. Kreise, and E. Recknagel, J. Chem. Phys. 85, 636 (1986).
25. E. J. Hart and M. Anbar, The Hydrated Electron (Wiley-Interscience, New York, 1970).
26. W. F. Schmidt, Can. J. Chem. 55, 2197 (1977).
27. J. Jortner, Ber. Bunsenges, Phys. Chem. 75, 696 (1971).
28. P. Han and D. M. Bartels, J. Phys. Chem. 94, 5824 (1990); p. 5828 has a background on water photophysics.
29. A. Henglein, Ber. Bunsenges, Phys. Chem. 78, 1078 (1975).
30. A. Henglein, Can. J. Chem. 55, 2112 (1977).
31. Yu V. Pleskov and Z. A. Rottenberg, J. Electoranal. Chem. 20, 1 (1969).
32. G. C. Barker, Ber. Bunsenges, Phys. Chem. 75, 728 (1971).
33. A. M. Brodsky and Yu V. Pleskov, Prog. Surface Sci. 2, 1 (1972).
34. K. Yamashita and H. Imai, Bull. Soc. Chim. Jpn. 45, 628 (1972).
35. J. K. Sass and H. Gerischer, in Photoemission and the Electronic Properties of Surfaces, edited by B. Feuerbacher, B. Fitton, and R. F. Willis (Wiley-Interscience, New York, 1978).
36. P. Lorrain and D. Corson, Electromagnetic Fields and Waves, 2nd ed. (W. H. Freeman, San Francisco, 1970), pp. 115-116.
37. Molar polarizabilities were calculated using the Clausius-Mossotti equation from Ref. 35 with index of refraction data and density from Ref. 12.
38. Calculated using the Clausius-Mossotti equation from Ref. 35, the dielectric constant for liquid methane from Ref. 12, and density from K. R. Ramaprasad, J. Caldwell, and D. S. McClure, Icarus 35, 400 (1978).
39. D. Vidal and M. Lallmand, J. Chem. Phys. 64, 4293 (1976).
40. W. Tauchen, H. Jungblut, and W. F. Schmidt, Can. J. Chem. 55, 1860 (1977).
41. J. J. P. Stewart, J. Comp. Chem. 10, 209 (1989).
42. J. J. P. Stewart, J. Comp. Chem. 10, 221 (1989).
43. HyperChem by Hypercube is a commercial software package which incorporates a friendly graphics interface with a variety of molecular modelling, semiempirical, and ab initio methods.
44. V. V. Vasilyev, Acta Chim. Hungarica 130, 743 (1993); these calculations to n = 16 have been reproduced and extended it to n = 136, M. D. Tissandier, A. D. Earhart, S. I. Muhammad, and J. V. Coe, in preparation: M. D. Tissandier, Ph.D. thesis, The Ohio State University (1997).
45. V. V. Vasilyev, Acta Chim. Hungarica 130, 743 (1993); these calculations to n = 16 have been reproduced and extended it to n = 136, M. D. Tissandier, A. D. Earhart, S. I. Muhammad, and J. V. Coe, in preparation: M. D. Tissandier, Ph.D. thesis, The Ohio State University (1997).
46. V. V. Vasilyev, Acta Chim. Hungarica 130, 743 (1993); these calculations to n = 16 have been reproduced and extended it to n = 136, M. D. Tissandier, A. D. Earhart, S. I. Muhammad, and J. V. Coe, in preparation: M. D. Tissandier, Ph.D. thesis, The Ohio State University (1997).
47. J. K. Gregory and D. C. Clary, J. Phys. Chem. 100, 18014 (1996).
48. K. Liu, J. D. Cruzan, and R. J. Saykally, Science 271, 929 (1996).
49. S. S. Xantheas and T. H. Dunning, J. Chem. Phys. 99, 8774 (1993).
50. S. S. Xantheas, J. Chem. Phys. 100, 7523 (1994).
51. F. Huisken, M. Kaloudis, and A. Kulcke, J. Chem. Phys. 104, 17 (1996).
52. J. K. Gregory, D. C. Clary, K. Liu, M. G. Brown, and R. J. Saykally, Science 275, 814 (1997).
53. C. J. Tsai and K. D. Jordan, Chem. Phys. Lett. 213, 181 (1993).
54. K. Liu, J. K. Gregory, M. G. Brown, C. Carter, R. J. Saykally, and D. C. Clary, Nature 381, 501 (1996).
55. J. Kim, B. J. Mhin, S. J. Lee, and K. S. Kim, Chem. Phys. Lett. 219 243 (1994).
56. C. Gruenloh, J. Carney, C. Arrington, T. S. Zwier, S. Y. Fredericks and K. D. Jordan, Science (in press).
57. s/T)/∂(1/T) determines the 0.226 eV value of the constant. 55 One could also use 0.443 eV for this constant to give a relation which roughly connects bulk to the calculated cluster values from I. P. Buffy and W. B. Brown, Chem. Phys. Lett. 109, 59 (1984), avoiding the offset issue.
58. s/T)/∂(1/T) determines the 0.226 eV value of the constant. 55 One could also use 0.443 eV for this constant to give a relation which roughly connects bulk to the calculated cluster values from I. P. Buffy and W. B. Brown, Chem. Phys. Lett. 109, 59 (1984), avoiding the offset issue.
59. H. A. Schwarz and R. W. Dodson, J. Phys. Chem. 88, 3643 (1984).
60. T. A. Milne, J. E. Beachey, and F. T. Greene, AFCRL Report 70-0341 (1970).
61. n clusters.
62. 0 and the known optical polarizability of water, see the last paragraph of Sec. II A.
63. w) vs 1/T.
64. U. Sokolov and G. Stein, J. Chem. Phys. 44, 3329 (1966).
65. J. W. Boyle, J. A. Ghormley, C. J. Hochanadel, and J. F. Riley, J. Phys. Chem. 73, 2886 (1969).
66. The adiabatic energetic threshold determined in this work for seeing a hydrated electron from photoexcitation of water is 5.3 eV, so the observed threshold of 6.5 eV lies 1.2 eV above the minimum hydrated electron energy level, but 6.5 eV is not enough to access the conduction band, particularly when the associated reorganization energies are considered (see Fig. 5). The 10.06 eV PET of water suggests that 6.5 eV photons are about 3.6 eV shy of reaching the conduction band which is even too far to invoke electron-trapping states (however, lower values of the PET can change these arguments).
67. G. P. Parravicini and L. Resca, Phys. Rev. B 8,. 3009 (1973); Ref. 18 in this work explains that conduction bands were not calculated, but also how they might have been.
68. B. Baron and F. Williams, J. Chem. Phys. 64, 3896 (1976).
69. B. Baron, D. Hoover, and F. Williams, J. Chem. Phys. 68, 1997 (1978).
70. M. J. Campbell, J. Liesegang, J. D. Riley, R. C. G. Leckey, and J. G. Jenkin, J. Electron Spectry. Relat. Phenom. 15, 83 (1979).
71. Figure 2 in the present work shows why the photoemission threshold of water does not determine the vacuum level as tentatively assumed in Fig. 3 of Ref. 8.
72. J. Hart and W. C. Gottschall, J. Am. Chem. Soc. 71, 2102 (1967).
73. L. Kevan, J. Phys. Chem. 76, 3830 (1972).
74. R. Onaka and T. Takahashi, J. Phys. Soc. Jpn. 24, 548 (1968).
75. T. Shibaguchi, H. Onuki, and R. Onaka, J. Phys. Soc. Jpn. 42, 152 (1977).