Spin-orbit Effects on the Structure of Haloiodomethane Cations CH2XI+ (X=F, Cl, Br, and I)

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The importance of including spin-orbit interactions, for the correct description of structures and vibrational frequencies of haloiodomethanes is demonstrated by density functional theory. calculations with spin-orbit relativistic effective core potentials (SO-DFT). The vibrational frequencies and the molecular geometries obtained by SO-DFT calculations do not match with the experimental results as well as for other cations without significant relativistic effects. In this sense, the present data can be considered as a guideline in the development of the relativistic quantum chemical methods. The influence of spin-orbit effects on the bending frequency of the cation could well be recognized by comparing the experimental and calculated results for CH2BrI and CH2ClI cations. Spin-orbit effects on the geometries and vibrational frequencies of CH2XI (X=F, Cl, Br, and I) neutral are negligible except that C-I bond lengths of haloiodomethane neutral is slightly increased by the inclusion of spin-orbit effects. The (2)A' and (2)A '' states were found in the cations of haloiodomethanes and mix due to the spin-orbit interactions and generate two E-2(1/2) fine-structure states. The geometries of CH2XI+ (X=F and Cl) from SO-DFT calculations are roughly in the middle of two cation geometries from DFT calculations since two cation states of CH2XI (X=F and Cl) from DFT calculations are energetically close enough to mix two cation states. The geometries of CH2XI+ (X=Br and I) from SO-DFT calculations are close to that of the most stable cation from DFT calculations since two cation states of CH2XI (X=Br and I) from DFT calculations are energetically well separated near the fine-structure state minimum.
Publisher
KOREAN CHEMICAL SOC
Issue Date
2014-03
Language
English
Article Type
Article
Keywords

DENSITY-FUNCTIONAL THEORY; EFFECTIVE CORE POTENTIALS; THRESHOLD-IONIZATION SPECTROSCOPY; RELATIVISTIC EFFECTIVE POTENTIALS; TIME PHOTODISSOCIATION DYNAMICS; MARINE BOUNDARY-LAYER; AB-INITIO; CHLOROIODOMETHANE CATION; CORRELATION-ENERGY; IODINE

Citation

BULLETIN OF THE KOREAN CHEMICAL SOCIETY, v.35, no.3, pp.775 - 782

ISSN
0253-2964
DOI
10.5012/bkcs.2014.35.3.775
URI
http://hdl.handle.net/10203/188949
Appears in Collection
CH-Journal Papers(저널논문)
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