rotational and renner-teller analyses of the ground and excited state levels of the jet-cooled cs 2...
Post on 11-Jan-2016
219 Views
Preview:
TRANSCRIPT
ROTATIONAL AND RENNER-TELLER ANALYSES OF THE GROUND AND EXCITED STATE LEVELS
OF THE JET-COOLED CS2 ION
Dennis J. Clouthier & Sheng-Gui HeDepartment of ChemistryUniversity of Kentucky
Lexington, KY 40506-0055
Discharge Jet Spectroscopy
Molecules:
SiH2, SiF2, SiCl2, HSiF, HSiCl, HSiBr, HSiI, H2C=Si
GeH2, GeF2, GeCl2, HGeCl, HGeBr, HGeI, H2C=Ge
Free Radicals:
SiCH, SiCCl, GeCH, Ge2, FS2, HPCl, HPBr, BS2
BF2, BCl2, HBF, HBCl, HBBr, HCCS, HCCSe
Ions:
???
Jet-Cooled Ions Detected by LIF
Cations
CO2+, N2O+, C6F6
+, HCP+, CS2+
Anions
SCCSˉ
S2ˉ ?
M. Nakajima, Y. Yoneda, Y. Sumiyoshi, T. Nagata, and Y. Endo, J. Chem. Phys. 119, 7805 (2003)
CS2+ History
Low resolution emission spectra (Barrow, 1950)
B-X high resolution emission spectra (Callomon, 1958)
A-X medium resolution emission spectra (Balfour, 1976)
Matrix studies of LIF and emission spectra (Bondybey, 1980)
Photoelectron spectra of X and A state vibronic levels (Ng, 1997, 2001)
No LIF or emission spectra of jet-cooled CS2+ or Renner-
Teller fit.
~
~
~ ~
~
~
CS2+ MO’s and
Structures
2u2g
…(2u)4 (2g)3 X 2g
~…(2u)3 (2g)4 A 2u
~
r" = 1.5554(10) r' = 1.6172(12)
Major Fitted Constants
Parameter
X A
ExperimentAb
InitioExperiment
Ab Initio
1 655.0(12) --- 582.00(47) 576.8
2 355.41(67) 345.4 303.07(44) 297.0
-0.1719(24) -0.1782 0.1221(57) 0.251
A -467.00(48) -446 -177.0(97) -173.6
W1 18.778(76) 15.803(39) ---
W2 1.07(31) --- ---
rms 1.62 0.56
~~
Comparison of CS2+ and
BS2
Parameter
X A
CS2+ BS2 CS2
+ BS2
1 655.0(12) 544.58 582.00(47) 512.71
2 355.41(67) 284.00 303.07(44) 309.49
-0.1719(24) -0.2119 0.1221(57) 0.0143
A -467.00(48) -414.43 -177.0(97) -259.47
W1 18.778(76) 19.213 15.803(39) 14.119
W2 1.07(31) 0.950 --- ---
rms 1.62 2.15 0.56 0.49
~~
PFI-PE Spectra
J. Liu et al., J. Phys. Chem. A, 105, 2183 (2001) measured extensive PFI-PE spectra of CS2 CS2
+ (A 2u) at ±4 cm-1 resolution.
Spectra assigned based on ab initio potential.
We have reanalyzed spectrum using our assignments.
Fit 45 energy levels to rms of 2.17 cm-1.
Derived constants in good agreement with more precise LIF constants.
~
top related