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Thiazyl chloride: an experimental and theoretical study of the valence shell HeI photoelectron spectrum
- Source :
- Chemical Physics, Chemical Physics, Elsevier, 2003, 288 (2-3), pp.95-104. ⟨10.1016/S0301-0104(02)00966-7⟩, Chemical Physics, 2003, 288 (2-3), pp.95-104. ⟨10.1016/S0301-0104(02)00966-7⟩
- Publication Year :
- 2003
- Publisher :
- Elsevier BV, 2003.
-
Abstract
- High level (CASSCF-MRCI) ab initio calculations are used to investigate the structural, electronic and vibrational properties of the electronic ground state of thiazyl chloride (NSCl) and of the low-lying electronic states of NSCl + . A new high resolution HeI photoelectron spectrum of NSCl has been recorded in the 10–16 eV energy region. From the results of the calculations, the first band is assigned to the (1) 2 A ′ state of NSCl + . The second one corresponds to the (2) 2 A ′ and (1) 2 A ″ states which are quasi-degenerate. Despite the high resolution, the two first bands show no vibrational fine structure. For the first one, Franck–Condon analysis shows that it is due to the overlapping of two vibrational progressions involving the S–Cl stretching and the NSCl bending modes. In the case of the second band, it is explained by the highly repulsive character of the potential energy surfaces of two states of NSCl + in the Franck–Condon region of the neutral molecule. For the third band, which shows vibrational peaks, the calculation of Franck–Condon factors permits the determination of the adiabatic ionisation energy of the (3) 2 A ′ electronic state of NSCl + at 13.798 eV. Finally, the fourth band, which is due to three different ionic states with vibrational progressions, is too complicated to be assigned quantitatively.
- Subjects :
- progressions
010304 chemical physics
Photoemission spectroscopy
Chemistry
electronic
General Physics and Astronomy
Ionic bonding
high
010402 general chemistry
01 natural sciences
Potential energy
0104 chemical sciences
nscl
constant
Ab initio quantum chemistry methods
0103 physical sciences
[PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Physical and Theoretical Chemistry
Atomic physics
Ionization energy
Valence electron
Adiabatic process
Ground state
energy
Subjects
Details
- ISSN :
- 03010104
- Volume :
- 288
- Database :
- OpenAIRE
- Journal :
- Chemical Physics
- Accession number :
- edsair.doi.dedup.....eed39bea55ab25864b0bef0f15660290