Ground and excited states of PtH and PtH/sup +/ by relativistic ab initio electronic structure calculations: A model study for hydrogen chemisorption on platinum surfaces and related photoemission properties

Journal Article · Sat Oct 15 04:00:00 EDT 1983 · J. Chem. Phys.; (United States)

OSTI ID:5667367

Wang, S W; Pitzer, K S

Relativistic electronic structure calculations for the ground and excited states of PtH and PtH/sup +/ are performed using first a spin-averaged relativistic effective core potential (AREP) at the self-consistent field (SCF) level and later incorporating the spin dependence at the configuration interaction (CI) level. These calculations lead to several conclusions: (1) Both the 6s and 5d orbitals of Pt interact strongly with the H orbitals, clearly indicating that the bonding involves both 6s and 5d electrons. (2) Correlation energies contribute significantly to the PtH binding energy but have little effect on the force constant. (3) The polarization functions centered on H are much more important than those centered on Pt in affecting the binding energy. (4) The two lowest states /sup 2/..delta../sub 5/2/ and /sup 2/..sigma../sub 1/2/ are calculated to have almost exactly the same energy; either may be the lower one. The lowest 3/2 state is mixed /sup 2/(..pi..+..delta..)/sub 3/2/ and lies a little higher in energy. (5) Both the first ionization potential and the ionization energy of the H-like level agree reasonably well with the experimental data. Finally, the absolute binding energy of PtH is 2.45 eV, to be compared with the experimental value of 3.44 eV. The discrepancy is due to our computational limitations.

• Research Organization: Department of Chemistry and Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
• OSTI ID: 5667367
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 79:8; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
CHARGED PARTICLES
CHEMICAL REACTIONS
CHEMISORPTION
ELECTRONIC STRUCTURE
ELEMENTS
EMISSION
ENERGY LEVELS
EXCITED STATES
FIELD THEORIES
GENERAL RELATIVITY THEORY
GROUND STATES
HYDRIDES
HYDROGEN COMPOUNDS
IONS
METALS
MOLECULAR IONS
PHOTOEMISSION
PLATINUM
PLATINUM COMPOUNDS
PLATINUM HYDRIDES
PLATINUM METALS
RELATIVITY THEORY
SECONDARY EMISSION
SEPARATION PROCESSES
SORPTION
SORPTIVE PROPERTIES
SURFACE PROPERTIES
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS