Molecular beam photoionization study of HgCl/sub 2/

Journal Article · Sat Jan 01 00:00:00 EST 1983 · J. Chem. Phys.; (United States)

OSTI ID:6635433

Linn, S H; Brom, Jr, J M; Tzeng, W; Ng, C Y

High resolution (0.14 A FWHM) photoionization efficiency (PIE) data for HgCl/sup +//sub 2/ have been obtained in the region 730--1100 A using an oven-type supersonic beam source. The ionization energies of the spin-orbit states X /sup 2/Pi/sub 3/2g/ and /sup 2/Pi/sub 1/2g/ were determined to be 11.380 +- 0.003 and 11.505 +- 0.003 eV, respectively. The major fragment ions observed in the region 600--1300 A are HgCl/sup +/, Hg/sup +/, and Cl/sup +/ having appearance energies of < or =11.041, 12.594 +- 0.018, and 16.721 +- 0.032 eV, respectively. The latter value allows the calculation of the bond dissociation energy for HgCl to be 21.1 +- 2.2 kcal/mol. This study further revealed members of autoionizing Rydberg series converging to the /sup 2/D/sub plus-or-minus5/2/ and /sup 2/D/sub plus-or-minus3/2,plus-or-minus1/2/ states at 16.715 +- 0.003 and 18.65 eV, respectively, which exhibit highly asymmetric Beutler--Fano line profiles. The comparison of the PIE curve for Hg/sup +/ from Hg and those for HgCl/sup +//sub 2/ and its fragments unambiguously shows that autoionizing Rydberg series resolved in this study can be assigned to transitions ((5d)/sup 10/sigma/sup 2//sub g/sigma/sup 2//sub u/..pi../sup 4//sub u/..pi../sup 4//sub g/) ..-->.. ((5d)/sup 9/sigma/sup 2//sub g/sigma/sup 2//sub u/..pi../sup 4//sub u/..pi../sup 4//sub g/ /sup 2/D/sub plus-or-minus5/2/) np and ((5d)/sup 10/sigma/sup 2//sub g/sigma/sup 2//sub u/..pi../sup 4//sub u/..pi../sup 4//sub g/) ..-->.. ((5d)/sup 9/sigma/sup 2//sub g/sigma/sup 2//sub u/..pi../sup 4//sub u/..pi../sup 4//sub g/ /sup 2/D/sub plus-or-minus3/2,plus-or-minus1/2/) np, n> or =6, which are mainly associated with the mercury atom in HgCl/sub 2/.

• Research Organization: Ames Laboratory, U. S. Department of Energy
• OSTI ID: 6635433
• Journal Information: J. Chem. Phys.; (United States), Vol. 78:1
• Country of Publication: United States
• Language: English

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
MERCURY CHLORIDES
DISSOCIATION ENERGY
PHOTOIONIZATION
AUTOIONIZATION
DISSOCIATION HEAT
ENERGY-LEVEL TRANSITIONS
MOLECULAR BEAMS
ULTRAVIOLET RADIATION
BEAMS
CHLORIDES
CHLORINE COMPOUNDS
ELECTROMAGNETIC RADIATION
ENERGY
ENTHALPY
HALIDES
HALOGEN COMPOUNDS
IONIZATION
MERCURY COMPOUNDS
MERCURY HALIDES
PHYSICAL PROPERTIES
RADIATIONS
REACTION HEAT
THERMODYNAMIC PROPERTIES
640301* - Atomic
Molecular &amp; Chemical Physics- Beams &amp; their Reactions