Ab-Initio Simulation Laboratory

Citation:

Wei, C. M., Gross A., & Scheffler M. (1998).  Ab initio calculation of the potential energy surface for the dissociation of H-2 on the sulfur-covered Pd(100) surface. Physical Review B. 57, 15572-15584., Jun, Number 24

Abstract:

The presence of sulfur atoms on the Pd(100) surface is known to hinder the dissociative adsorption of hydrogen. Using density-functional theory and the full-potential linear augmented plane-wave method, we investigate the potential energy surface (PES) of the dissociative adsorption of H-2 On the sulfur covered Pd(100) surface. The PES is changed significantly compared to the dissociation on the clean Pd(100) surface, particularly for hydrogen close to the S atoms. While the hydrogen dissociation at the clean Pd(100) surface is nonactivated, for the (2 x 2) sulfur adlayer (coverage Theta (S) = 0.25) the dissociation of H-2 is inhibited by energy barriers. Their heights strongly depend on the distance between the hydrogen and sulfur atoms leading to a highly corrugated PES. The largest barriers are in the vicinity of the sulfur atoms due to the strong repulsion between sulfur and hydrogen. Still the hydrogen dissociation on the (2x2) sulfur covered Pd(100) surface is exothermic. Thus the poisoning effect of sulfur adatoms for H-2 dissociation at low sulfur coverage (Theta(S) less than or equal to 0.25) is mainly governed by the formation of energy barriers, not by blocking of the adsorption sites. For the c(2 x 2) sulfur adlayer (Theta(S)= 0.5), the PES for hydrogen dissociation is purely repulsive. This is due to the fact that for all different possible adsorption geometries the hydrogen molecules come too close.to the sulfur adatoms before the dissociation is completed.

Notes:

ISI Document Delivery No.: ZY631Times Cited: 38Cited Reference Count: 35Cited References: BEHM RJ, 1980, SURF SCI, V99, P320, DOI 10.1016/0039-6028(80)90396-9 BLAHA P, WIEN95 BURKE ML, 1990, SURF SCI, V237, P1, DOI 10.1016/0039-6028(90)90515-A COMSA G, 1980, SURF SCI, V95, pL210, DOI 10.1016/0167-2584(80)90566-6 DARLING GR, 1994, SURF SCI, V304, P6461 Eichler A, 1998, SURF SCI, V397, P116, DOI 10.1016/S0039-6028(97)00724-3 Eichler A, 1996, PHYS REV LETT, V77, P1119, DOI 10.1103/PhysRevLett.77.1119 FEIBELMAN PJ, 1985, SURF SCI, V149, P48, DOI 10.1016/S0039-6028(85)80012-1 FEIBELMAN PJ, 1991, PHYS REV LETT, V67, P461, DOI 10.1103/PhysRevLett.67.461 FEIBELMAN PJ, 1984, PHYS REV LETT, V52, P61, DOI 10.1103/PhysRevLett.52.61 GOODMAN DW, 1981, SURF SCI, V105, pL265, DOI 10.1016/0167-2584(81)90065-7 Gross A, 1998, PHYS REV B, V57, P2493, DOI 10.1103/PhysRevB.57.2493 GROSS A, 1995, J CHEM PHYS, V102, P5045, DOI 10.1063/1.469554 GROSS A, 1995, PHYS REV LETT, V75, P2718, DOI 10.1103/PhysRevLett.75.2718 GROSS AF, UNPUB Hammer B, 1995, SURF SCI, V343, P211, DOI 10.1016/0039-6028(96)80007-0 HAMMER B, 1995, PHYS REV LETT, V74, P3487, DOI 10.1103/PhysRevLett.74.3487 HAMMER B, 1993, SURF SCI, V297, pL68, DOI 10.1016/0039-6028(93)90007-7 HAMMER B, 1994, PHYS REV LETT, V73, P1400, DOI 10.1103/PhysRevLett.73.1400 JOHNSON S, 1981, SURF SCI, V108, P77, DOI 10.1016/0039-6028(81)90359-9 Kohler B, 1996, COMPUT PHYS COMMUN, V94, P31, DOI 10.1016/0010-4655(95)00139-5 LUNDQVIST BI, 1979, SURF SCI, V89, P196, DOI 10.1016/0039-6028(79)90608-3 MACLAREN JM, 1986, SURF SCI, V165, pL80, DOI 10.1016/0039-6028(86)90804-6 NORSKOV JK, 1981, PHYS REV LETT, V46, P257, DOI 10.1103/PhysRevLett.46.257 NORSKOV JK, 1993, CHEM PHYSICS SOLID S, V6, P1 NORSKOV JK, 1984, SURF SCI, V137, P65, DOI 10.1016/0039-6028(84)90676-9 PERDEW JP, 1992, PHYS REV B, V46, P6671, DOI 10.1103/PhysRevB.46.6671 RENDULIC KD, 1989, SURF SCI, V208, P404, DOI 10.1016/0039-6028(89)90010-1 White JA, 1996, PHYS REV B, V53, P1667, DOI 10.1103/PhysRevB.53.1667 WHITE JA, 1994, PHYS REV LETT, V73, P1404, DOI 10.1103/PhysRevLett.73.1404 Wilke S, 1996, PHYS REV B, V53, P4926, DOI 10.1103/PhysRevB.53.4926 WILKE S, 1995, SURF SCI, V329, pL605, DOI 10.1016/0039-6028(95)00355-X Wilke S, 1996, PHYS REV LETT, V77, P1560, DOI 10.1103/PhysRevLett.77.1560 Wilke S, 1996, PHYS REV LETT, V76, P3380, DOI 10.1103/PhysRevLett.76.3380 WILKE S, UNPUBWei, CM Gross, A Scheffler, MAMER PHYSICAL SOCCOLLEGE PK

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