Experimental and ab initio characterization of HC 3 N + vibronic structure. II. High-resolution VUV PFI-ZEKE spectroscopy
Vacuum-ultraviolet pulsed-field-ionization zero-kinetic-energy photoelectron spectra of X Π2←XΣ+1 and B Π2←XΣ+1 transitions of the HC N and HC N isotopologues of cyanoacetylene have been recorded. The resolution of the photoelectron spectra allowed us to resolve the vibrational structures and the sp...
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| Published in | The Journal of chemical physics Vol. 145; no. 23; p. 234309 |
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| Main Authors | , , , , |
| Format | Journal Article |
| Language | English |
| Published |
United States
21.12.2016
|
| Online Access | Get more information |
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| Summary: | Vacuum-ultraviolet pulsed-field-ionization zero-kinetic-energy photoelectron spectra of X
Π2←XΣ+1 and B
Π2←XΣ+1 transitions of the HC
N and HC
N isotopologues of cyanoacetylene have been recorded. The resolution of the photoelectron spectra allowed us to resolve the vibrational structures and the spin-orbit splittings in the cation. Accurate values of the adiabatic ionization potentials of the two isotopologues (E
/hc(HC
N)=93 909(2) cm
and E
/hc(HC
N)=93 912(2) cm
), the vibrational frequencies of the ν
, ν
, and ν
vibrational modes, and the spin-orbit coupling constant (A
= -44(2) cm
) of the X
Π2 cationic ground state have been derived from the measurements. Using ab initio calculations, the unexpected structure of the B
Π2←XΣ+1 transition is tentatively attributed to a conical intersection between the A
and B
electronic states of the cation. |
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| ISSN: | 1089-7690 |