Electronic states and potential energy surfaces of PdH/sub 2/: Comparison with PtH/sub 2/

Journal Article · Wed Jun 01 04:00:00 EDT 1988 · J. Chem. Phys.; (United States)

OSTI ID:5265120

Balasubramanian, K; Feng, P Y; Liao, M Z

Complete active space MCSCF (CASSCF) followed by multireference singles and doubles configuration interaction (MRSDCI) calculations are carried out on 13 electronic states of PdH/sub 2/ and 9 electronic states of PdH/sup +/ . The bending potential energy surfaces of /sup 1/A/sub 1/ and /sup 3/A/sub 1/ electronic states were obtained. The /sup 1/A/sub 1/ surface contains two bent minima (theta/sub e/ = 30/sup 0/ and theta/sub e/ = 62/sup 0/) and a higher linear minimum separated by a saddle point. The /sup 3/A/sub 1/ surface is relatively flat in the region of the saddle point. The Pd(/sup 1/S/sub 0/ ) atom forms a weak complex with H/sub 2/ but inserts spontaneously into H/sub 2/ while the Pd(/sup 3/D/sub 3/ ) atom has to surmount a large barrier for insertion into H/sub 2/. The spin--orbit effects for the electronic states of PdH/sub 2/ are estimated through relativistic configuration interaction calculations of PdH/sup +/ whose d Mulliken population is close to that of the d population of PdH/sub 2/. The ground state of PdH/sub 2/ is found to be a weakly bound bent /sup 1/A/sub 1/ state with theta/sub e/ = 30/sup 0/ and r/sub e/ (Pd--H) = 1.67 A. The electronic state and potential energy surfaces of PdH/sub 2/ are compared with PtH/sub 2/. The Pt--H bond is found to be stronger than the Pd--H bond mainly due to relativistic effects. The Pd--H bonds are more ionic than the Pt--H bonds

• Research Organization: Department of Chemistry, Arizona State University, Tempe, Arizona 85287-1604
• OSTI ID: 5265120
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 88:11; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
BOND LENGTHS
CHEMICAL REACTIONS
CHEMISORPTION
CONFIGURATION INTERACTION
COUPLING
DIMENSIONS
ELECTRONIC STRUCTURE
ENERGY
FIELD THEORIES
GENERAL RELATIVITY THEORY
HYDRIDES
HYDROGEN COMPOUNDS
INTERMEDIATE COUPLING
L-S COUPLING
LENGTH
PALLADIUM COMPOUNDS
PALLADIUM HYDRIDES
PLATINUM COMPOUNDS
PLATINUM HYDRIDES
POTENTIAL ENERGY
RELATIVITY THEORY
SELF-CONSISTENT FIELD
SEPARATION PROCESSES
SORPTION
TRANSITION ELEMENT COMPOUNDS