High-resolution pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopic study of the two lowest electronic states of the ozone cation O3+.
نویسندگان
چکیده
The pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectrum of jet-cooled O3 has been recorded in the range 101,000-104,000 cm(-1). The origins of the X 1A1-->X+ 2A1 and X 1A1-->A+ 2B2 transitions could be determined from the rotational structure of the bands, the photoionization selection rules, the photoionization efficiency curve, and comparison with ab initio calculations. The first adiabatic ionization energy of O3 was measured to be 101,020.5(5) cm(-1) [12.524 95(6) eV] and the energy difference between the X+ 2A1 (0,0,0) and A+ 2B2 (0,0,0) states was determined to be DeltaT0=1089.7(4) cm(-1). Whereas the X-->X+ band consists of an intense and regular progression in the bending (nu2) mode observed up to v2+=4, only the origin of the X-->A+ band was observed. The analysis of the rotational structure in each band led to the derivation of the r0 structure of O3+ in the X+ [C2v,r0=1.25(2) A,alpha0=131.5(9) degrees ] and A+[C2v,r0=1.37(5) A,alpha0=111.3(38) degrees ] states. The appearance of the spectrum, which is regular up to 102,300 cm(-1), changes abruptly at approximately 102,500 cm(-1), a position above which the spectral density increases markedly and the rotational structure of the bands collapses. On the basis of ab initio calculations, this behavior is attributed to the onset of large-amplitude motions spreading through several local minima all the way to large internuclear distances. The ab initio calculations are consistent with earlier results in predicting a seam of conical intersections between the X+ and A+ states approximately 2600 cm(-1) above the cationic ground state and demonstrate the existence of potential minima at large internuclear distances that are connected to the main minima of the X+ and A+ states through low-lying barriers.
منابع مشابه
Selective field ionization of high Rydberg states: Application to zero-kinetic-energy photoelectron spectroscopy
Sequences of pulsed electric fields have been designed and tested that enable a higher selectivity in the pulsed field ionization of high Rydberg states (n>100) than has so far been possible. The enhanced selectivity originates from the permutation of the parabolic quantum numbers n1 and n2 that is induced by a sufficiently rapid inversion of the electric field polarity during a pulse sequence....
متن کاملZero kinetic energy-pulsed field ionization and resonance enhanced multiphoton ionization photoelectron spectroscopy: Ionization dynamics of Rydberg states in HBr
The results of rotationally resolved resonance enhanced multiphoton ionization photoelectron spectroscopy and zero kinetic energy-pulsed field ionization studies on HBr via various rotational levels of the F D2 and f D2 Rydberg states are reported. These studies lead to an accurate determination of the lowest ionization threshold as 94 098.961 cm. Observed rotational and spin–orbit branching ra...
متن کاملRotationally resolved photoelectron spectra in resonance enhanced multiphoton ionization of HCl via the F 12 Rydberg state
Articles you may be interested in Dynamics of high‐n Rydberg states employed in zero kinetic energy‐pulsed field ionization spectroscopy via the F 1Δ2, D 1Π1, and f 3Δ2 Rydberg states of HCl Resonance enhanced multiphoton ionization photoelectron spectroscopy and pulsed field ionization via the F 1Δ2(v'=0) and f 3Δ2(v'=0) Rydberg states of HCl
متن کاملHigh resolution study of low-lying correlation satellites below 25 eV in xenon probed by pulsed-field-ionization-zero-kinetic- energy photoelectron spectroscopy
متن کامل
Torsional vibrational structure of the propene radical cation studied by high-resolution photoelectron spectroscopy.
The pulsed-field-ionization zero-kinetic-energy photoelectron spectra of the X̃(+2)A(")←X̃(1)A' transition of CH(3)CHCH(2) (propene), CD(3)CDCD(2), and several partially deuterated isotopomers have been recorded in the region of their adiabatic ionization thresholds and up to 2000 cm(-1) of internal energy of the cations. The vibrational structure has been assigned on the basis of the frequency s...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
- The Journal of chemical physics
دوره 122 2 شماره
صفحات -
تاریخ انتشار 2005