Relativistic calculations of electronic states of PdH

Journal Article · Thu Oct 01 04:00:00 EDT 1987 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.452952· OSTI ID:6016386

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

Complete active space MCSCF(CASSCF)/first-order configuration interaction (FOCI) calculations followed by relativistic configuration interaction (RCI) calculations are carried out on /sup 2/..sigma../sup +/, /sup 2/Pi, /sup 2/..delta.., and /sup 2/..sigma../sup +/(II) lambda--s states and 1/2, 3/2, 1/2(II), 3/2(II), and 5/2 ..omega..--..omega.. states of PdH. Our calculations predict that the ground state is /sup 2/..sigma../sup +//sub 1/2/. The spin--orbit splitting and contamination of the excited states (/sup 2/Pi and /sup 2/..delta..) are quite large. The two 3/2 states are quite mixed (3/2(I): 66% /sup 2/..delta../sub 3//sub ///sub 2/, 29% /sup 2/Pi/sub 3//sub ///sub 2/) in character. The spectroscopic properties (R/sub e/, T/sub e/, D/sub e/, and ..omega../sub e/) of all the above states are calculated and compared with available experimental results on the ground state of PdD. The Mulliken population analysis of the low-lying states of PdH shows that the /sup 2/..sigma../sup +/ state is ionic (Pd/sup +/H/sup -/) but the excited /sup 2/Pi and /sup 2/..delta.. states are a bit more ionic with the same polarity as the ground state. The 3/2 state exhibits an interesting avoided crossing.

• Research Organization: Department of Chemistry, Arizona State University, Tempe, Arizona 85287
• OSTI ID: 6016386
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 87:7; 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
CONFIGURATION INTERACTION
CORRECTIONS
COUPLING
ELECTRONIC STRUCTURE
FUNCTIONS
HYDRIDES
HYDROGEN COMPOUNDS
INTERMEDIATE COUPLING
L-S COUPLING
PALLADIUM COMPOUNDS
PALLADIUM HYDRIDES
RADIATIVE CORRECTIONS
SPECTRAL FUNCTIONS
TRANSITION ELEMENT COMPOUNDS