SPECTROSCOPY AND ELECTRONIC-STRUCTURE OF JET-COOLED NIPD AND PDPT

被引:46
作者
TAYLOR, S
SPAIN, EM
MORSE, MD
机构
[1] Department of Chemistry, University of Utah, Salt Lake City
关键词
D O I
10.1063/1.457917
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Resonant two-photon ionization spectroscopy of jet-cooled NiPd and PdPt has revealed a dense vibronic spectrum for NiPd and a much more sparse spectrum for PdPt. Four vibrational progressions have been identified for NiPd, and three have been located for PdPt. High resolution investigations of NiPd have established a ground state bond length of r″0 = 2.242 ± 0.005 Å with Ω″ = 2. The observed spectra have been used to bracket the ionization potentials, giving IP(NiPd) = 7.18 ± 0.76 eV and IP(PdPt) = 8.27 ± 0.38 eV. In contrast to previous work on Ni 2, NiPt, and Pt2, no abrupt onset of rapid predissociation is observed for either NiPd or PdPt. A discussion of this result in terms of the expected potential energy curves for the palladium-containing diatomics is presented, which when combined with the frequencies of the highest energy vibronic bands observed yields estimates of D0(NiPd) ≈ 1.46 eV and D0(PdPt) ≈ 1.98 eV. The lack of observable vibronic transitions in Pd2 above 11 375 cm-1 places D0(Pd 2) below 1.41 eV, in agreement with Knudsen effusion mass spectrometry. Finally a comparison of the platinum group dimers and the coinage metal dimers is given, demonstrating the increasing importance of d-orbital contributions to the bonding in the platinum group dimers as one moves down the periodic table. The anomalous behavior of the palladium-containing diatomics is also discussed in terms of the highly stable 4d10 5s0, 1S0 ground state of atomic palladium. © 1990 American Institute of Physics.
引用
收藏
页码:2710 / 2720
页数:11
相关论文
共 37 条
[11]   ABSOLUTE IODINE (I-2) STANDARDS MEASURED BY MEANS OF FOURIER-TRANSFORM SPECTROSCOPY [J].
GERSTENKORN, S ;
LUC, P .
REVUE DE PHYSIQUE APPLIQUEE, 1979, 14 (08) :791-794
[12]  
Gerstenkorn S., 1978, ATLAS SPECTRE ABSORP
[13]  
Herzberg G., 1950, MOL SPECTRA MOL STRU, P315
[14]   ATOMIZATION ENTHALPIES OF THE MOLECULES CU-3, AG-3, AND AU-3 [J].
HILPERT, K ;
GINGERICH, KA .
BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1980, 84 (08) :739-745
[15]  
Kaldor A., 1988, ADV CHEM PHYS, V70, P211, DOI DOI 10.1002/9780470122693.CH6
[16]   STABILITY AND THERMODYNAMICS OF LIGAND-FREE GERMANIUM-GOLD CLUSTERS [J].
KINGCADE, JE ;
CHOUDARY, UV ;
GINGERICH, KA .
INORGANIC CHEMISTRY, 1979, 18 (11) :3094-3104
[17]   ATOMIZATION ENERGIES AND HEATS OF FORMATION OF GASEOUS AU2, TB2, TBAU, HOAU, TBAU2, AND HOAU2 [J].
KORDIS, J ;
GINGERICH, KA ;
SEYSE, RJ .
JOURNAL OF CHEMICAL PHYSICS, 1974, 61 (12) :5114-5121
[18]   THEORETICAL ASPECTS OF METAL ATOM CLUSTERS [J].
KOUTECKY, J ;
FANTUCCI, P .
CHEMICAL REVIEWS, 1986, 86 (03) :539-587
[19]   ABINITIO STUDIES OF TRANSITION-METAL SYSTEMS [J].
LANGHOFF, SR ;
BAUSCHLICHER, CW .
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, 1988, 39 :181-212
[20]   DISSOCIATION ENERGY OF PD2 [J].
LIN, SS ;
STRAUSS, B ;
KANT, A .
JOURNAL OF CHEMICAL PHYSICS, 1969, 51 (05) :2282-&