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Title: Molecular beam photoionization study of HgBr/sub 2/ and HgI/sub 2/

Abstract

Photoionization efficiency (PIE) data for HgBr/sub 2//sup +/ and HgI/sub 2//sup +/ and their fragment ions have been obtained in the region 600--1350 A using an oven-type supersonic beam source. The ionization energies (IE) for the X /sup 2/Pi/sub 3/2g/ states of HgBr/sub 2//sup +/ and HgI/sub 2//sup +/ were determined to be 10.560 +- 0.003 and 9.5088 +- 0.0022 eV, respectively. The analyses of the Rydberg series converging to the /sup 2/Pi/sub 1/2g/ states of HgBr/sub 2//sup +/ and HgI/sub 2//sup +/ yield a value of 10.8846 +- 0.0012 eV for the IE of the /sup 2/Pi/sub 1/2g/ state of HgBr/sub 2//sup +/ and 10.1953 +- 0.0025 eV for that of HgI/sub 2//sup +/. The major fragment ions from HgBr/sub 2/ were identified to be HgBr/sup +/, Hg/sup +/, Br/sub 2//sup +/, and Br/sup +/ and those from HgI/sub 2/ were found to be HgI/sup +/, I/sub 2//sup +/, and I/sup +/. The measured appearance energies for HgBr/sup +/ and HgI/sup +/ allow the calculation of the bond dissociation energies for HgBr/sup +/ and HgI/sup +/ to be 55 +- 2 and 59 +- 1 kcal/mol, respectively. Similar to the observation in the PIE curves for HgCl/sub 2//sup +/more » and its fragment ions, the PIE spectra for HgBr/sub 2//sup +/, HgI/sub 2//sup +/, and their fragment ions are dominated by autoionization structures exhibiting asymmetric Beutler--Fano line profiles. The comparison of the PIE curves of HgCl/sub 2//sup +/, HgBr/sub 2//sup +/, HgI/sub 2//sup +/, and Hg/sup +/ from Hg confirms the previous conclusion that these autoionizing Rydberg series can be assigned to transitions((5d)/sup 10/sigma/sub g//sup 2/sigma/sub u//sup 2/..pi../sub u//sup 4/..pi../sub g//sup 4/) ..-->.. ((5d)/sup 9/sigma/sub g//sup 2/sigma/sub u//sup 2/..pi../sub u//sup 4/..pi../sub g//sup 4/ /sup 2/D/sub plus-or-minus5/2/)np and ((5d)/sup 10/sigma/sub g//sup 2/sigma/sub u//sup 2/..pi../sub u//sup 4/..pi../sub g//sup 4/) ..-->.. ((5d)/sup 9/sigma/sub g//sup 2/sigma/sub u//sup 2/..pi../sub u//sup 4/..pi../sub g//sup 4/ /sup 2/D/sub plus-or-minus3/2,tsplus-or-minus1/2/)np, n> or =6, which are mainly associated with the mercury atom in HgX/sub 2/, X = Cl, Br, and I.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Ames Laboratory, U.S. Department of Energy, and Department of Chemistry, Iowa State University, Ames, Iowa 50011
OSTI Identifier:
6635298
Resource Type:
Journal Article
Journal Name:
J. Chem. Phys.; (United States)
Additional Journal Information:
Journal Volume: 78:1
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; MERCURY BROMIDES; PHOTOIONIZATION; MERCURY IODIDES; DISSOCIATION; EFFICIENCY; MOLECULAR BEAMS; BEAMS; BROMIDES; BROMINE COMPOUNDS; HALIDES; HALOGEN COMPOUNDS; IODIDES; IODINE COMPOUNDS; IONIZATION; MERCURY COMPOUNDS; MERCURY HALIDES; 640302* - Atomic, Molecular & Chemical Physics- Atomic & Molecular Properties & Theory

Citation Formats

Linn, S H, Tzeng, W, Brom, Jr, J M, and Ng, C Y. Molecular beam photoionization study of HgBr/sub 2/ and HgI/sub 2/. United States: N. p., 1983. Web.
Linn, S H, Tzeng, W, Brom, Jr, J M, & Ng, C Y. Molecular beam photoionization study of HgBr/sub 2/ and HgI/sub 2/. United States.
Linn, S H, Tzeng, W, Brom, Jr, J M, and Ng, C Y. 1983. "Molecular beam photoionization study of HgBr/sub 2/ and HgI/sub 2/". United States.
@article{osti_6635298,
title = {Molecular beam photoionization study of HgBr/sub 2/ and HgI/sub 2/},
author = {Linn, S H and Tzeng, W and Brom, Jr, J M and Ng, C Y},
abstractNote = {Photoionization efficiency (PIE) data for HgBr/sub 2//sup +/ and HgI/sub 2//sup +/ and their fragment ions have been obtained in the region 600--1350 A using an oven-type supersonic beam source. The ionization energies (IE) for the X /sup 2/Pi/sub 3/2g/ states of HgBr/sub 2//sup +/ and HgI/sub 2//sup +/ were determined to be 10.560 +- 0.003 and 9.5088 +- 0.0022 eV, respectively. The analyses of the Rydberg series converging to the /sup 2/Pi/sub 1/2g/ states of HgBr/sub 2//sup +/ and HgI/sub 2//sup +/ yield a value of 10.8846 +- 0.0012 eV for the IE of the /sup 2/Pi/sub 1/2g/ state of HgBr/sub 2//sup +/ and 10.1953 +- 0.0025 eV for that of HgI/sub 2//sup +/. The major fragment ions from HgBr/sub 2/ were identified to be HgBr/sup +/, Hg/sup +/, Br/sub 2//sup +/, and Br/sup +/ and those from HgI/sub 2/ were found to be HgI/sup +/, I/sub 2//sup +/, and I/sup +/. The measured appearance energies for HgBr/sup +/ and HgI/sup +/ allow the calculation of the bond dissociation energies for HgBr/sup +/ and HgI/sup +/ to be 55 +- 2 and 59 +- 1 kcal/mol, respectively. Similar to the observation in the PIE curves for HgCl/sub 2//sup +/ and its fragment ions, the PIE spectra for HgBr/sub 2//sup +/, HgI/sub 2//sup +/, and their fragment ions are dominated by autoionization structures exhibiting asymmetric Beutler--Fano line profiles. The comparison of the PIE curves of HgCl/sub 2//sup +/, HgBr/sub 2//sup +/, HgI/sub 2//sup +/, and Hg/sup +/ from Hg confirms the previous conclusion that these autoionizing Rydberg series can be assigned to transitions((5d)/sup 10/sigma/sub g//sup 2/sigma/sub u//sup 2/..pi../sub u//sup 4/..pi../sub g//sup 4/) ..-->.. ((5d)/sup 9/sigma/sub g//sup 2/sigma/sub u//sup 2/..pi../sub u//sup 4/..pi../sub g//sup 4/ /sup 2/D/sub plus-or-minus5/2/)np and ((5d)/sup 10/sigma/sub g//sup 2/sigma/sub u//sup 2/..pi../sub u//sup 4/..pi../sub g//sup 4/) ..-->.. ((5d)/sup 9/sigma/sub g//sup 2/sigma/sub u//sup 2/..pi../sub u//sup 4/..pi../sub g//sup 4/ /sup 2/D/sub plus-or-minus3/2,tsplus-or-minus1/2/)np, n> or =6, which are mainly associated with the mercury atom in HgX/sub 2/, X = Cl, Br, and I.},
doi = {},
url = {https://www.osti.gov/biblio/6635298}, journal = {J. Chem. Phys.; (United States)},
number = ,
volume = 78:1,
place = {United States},
year = {Sat Jan 01 00:00:00 EST 1983},
month = {Sat Jan 01 00:00:00 EST 1983}
}