Configuration interaction calculations of low-lying electronic states of O2,O2+, and O22+

Beebe, Nelson H. F.; Thulstrup, Erik W.; Andersen, Amanda

doi:10.1063/1.432433

Cited by 176 publications

(66 citation statements)

References 37 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Therefore, if a vibrational level of an ionic state coincides with an autoionization state which has an appropriate absorption cross section from the ground state, the TPES signal of the level may be observed even if the Franck-Condon factor for the direct PES transition is too small. Configuration interaction calculations of low-lying electronic states of O 2 ϩ were reported by Beebe et al 6 They suggested that in addition to the X 2 ⌸ g , A 2 ⌸ u and a 4 ⌸ u states, four other bound states which dissociate to the first dissociation limit are possible, that is, 2 ⌺ u ϩ , 4 ⌺ g ϩ , 6 ⌺ u ϩ and 4 ⌸ g , and they gave predicted spectroscopic constants (T e ,r e ,w e ,D e ) of these states. Yeager et al 7 calculated the ionization energies and the potential curves of seven lower states of O 2 ϩ .…”

Section: Introductionmentioning

confidence: 82%

“…Possible states which may arise from this limit are 2,4,6 ⌺ g,u ϩ , 2,4,6 ⌸ g,u . The potential energy curves for these states were calculated by Beebe et al 6 The 4 ⌸ g state has been well investigated by many authors. [21][22][23][24][25] We cannot recognize, in the present experiment, the 4 ⌸ g state which is predicted to have a shallow minimum.…”

Section: New Statesmentioning

confidence: 99%

See 1 more Smart Citation

High resolution threshold photoelectron spectrum of oxygen in the 12–19 eV region

Akahori¹,

Morioka

Tanaka

et al. 1997

The Journal of Chemical Physics

View full text Add to dashboard Cite

The threshold photoelectron spectrum of oxygen has been measured with high resolution in the photon energy range of 12-19 eV using a penetrating field technique and a synchrotron radiation source. The long vibrational progression of the X 2 ⌸ g state of O 2 ϩ was observed to vЈϭ45. An extrapolation in a Birge-Sponer plot (⌬G versus vЈϩ1/2) gives a maximum vibrational level v max Ј ϭ56. The A 2 ⌸ u state was also measured in detail. Most vibrational levels of the A 2 ⌸ u state of O 2 ϩ ͑from vЈϭ0 to 24͒ were observed for the first time. A Birge-Sponer plot of the A 2 ⌸ u state gives a maximum vibrational level v max Ј ϭ31. The dissociation limit of the A 2 ⌸ u state is slightly higher ͑76 meV͒ than the well-known dissociation limit O( 3 P 2 )ϩO ϩ ( 3 S 0 ) 18.733 eV. Therefore the A 2 ⌸ u state may be considered to have a hump. We observed new states which were assigned to 4 ⌺ g ϩ and 2 ⌺ u ϩ according to a previous theoretical investigation ͓Beebe et al., J. Chem. Phys. 64, 2080 ͑1976͔͒. Potential curves of the X 2 ⌸ g and A 2 ⌸ u states were calculated by the Rydberg-Klein-Rees method using both the rotational constants obtained previously by others ͓K. P. Huber and G. Herzberg, Molecular Spectra and Molecular Structure, Constants of Diatomic Molecules Volume IV ͑Van Nostrand, New York, 1974͔͒ and the vibrational energy values observed in the present experiment. A Le Roy-Bernstein plot as well as a Birge-Sponer plot were used to determine the dissociation energy of the X 2 ⌸ g state. However, the plot gave an unreasonably large dissociation limit.

show abstract

Section: Introductionmentioning

confidence: 82%

Section: New Statesmentioning

confidence: 99%

High resolution threshold photoelectron spectrum of oxygen in the 12–19 eV region

Akahori¹,

Morioka

Tanaka

et al. 1997

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…78 Being an open shell molecule, the multiplicaties for electronic states of 02 and its cation are complicated. The description of excitred 02 states, especially in the innervalence region (19-30 eV) at energies above the dissociation energy of 02 (18.733 eV), requires extensive configuration interaction (CIs).…”

Section: Rotational-resolved Pfi-pe Bands Formentioning

confidence: 99%

Advances in Photoionization and Photoelectron Studies Using Third Generation Synchrotron Radiation and Uv/Vuv Lasers

2000

Photoionization and Photodetachment

View full text Add to dashboard Cite

394 Photoionization and Photodetachment Downloaded from www.worldscientific.com by NANYANG TECHNOLOGICAL UNIVERSITY on 09/30/15. For personal use only. Advances in Photoionization and Photoelectron Studies ... 395 2.3.3. Rotational-resolved PFI-PE bands for Oa (b4E9 , 22IIu, B2Ey 2Eu , c4E) 437 2.3.3.1 . O (b4Ey,v += 0-9) 438 2.3.3.2. O2 (B2E; , v+ = 0 -7) 449 2.3.3.3. O (22IIu , 2E,.) 461 2.3.3.4. O9 (c4Eu , v+ = 0,1) 467 2.3.4. Rotational-resolved PFI-PE Bands for H2 (X2E9v+ = 0 -18) 474 2.3.5. Satellite States of Xe+ at 23-25 eV 482 2.4. Threshold Photoelectron-Photoion Coincidence Study 485 2.4.1. SFs+ 485 3. UV/VUV Laser Studies 489 3.1. Experimental Considerations 489 3.1.1. VUV-PIE and VUV-PFI-PE Measurements 489 3.1.2. N2P-PIE and N2P-PFI-PE Measurements 491 3.2. CS2 (X2113 /2,1/2; vi , v2 , v3) 491 3.2.1. Stark and VUV-PIE Spectra 492 3.2.2. VUV-PFI-PE Spectrum 497 3.2.3. Vibronic Band Intensities of VUV-PFI-PE, N2P-PFI-PE, and TPE Spectra 502 3.3. CH3SH+, CH3CH2SH+, and CH3SCH3 503 3.3.1. Ab initio Calculations 504 3.3.2. N2P-PIE and N2P-PFI-PE Spectra for CH3SH and CH3CH2SH 504 3.3.2.1. CH3SH+ 504 3.3.2.2 . CH3CH2SH+ 507 3.3.3. VUV-PFI-PE Spectra of CH3SH and CH3CH2SH 514 3.3.4. VUV-PFI-PE and N2P-PFI-PE Spectra for CH3SCH3 521 4. Conclusions and Future Developments 528 Acknowledgments 531 References 531 Photoionization and Photodetachment Downloaded from www.worldscientific.com by NANYANG TECHNOLOGICAL UNIVERSITY on 09/30/15. For personal use only.Parallel to the development of TPE spectroscopic techniques using cw VUV light sources, photoelectron studies using pulsed laser based techniques have achieved resolutions close to the optical bandwidth by employing the delayed pulsed field ionization (PFI)-photoelectron (PFI-PE) method .7,26,27 This method, pioneered by Dethlef and Schlag , is becoming the method of choice for laser based photoelectron studies . The PFI-PE Photoionization and Photodetachment Downloaded from www.worldscientific.com by NANYANG TECHNOLOGICAL UNIVERSITY on 09/30/15. For personal use only. high-n (n > 100) Rydberg states populated by laser excitation. Since these high-n Rydberg states converge to the IE of interest , the observed PFI-PE peak is slightly below the true IE. In addition to single -photon excitation using VUV lasers, excitation to high-n Rydberg states can also be accomplished by resonant or non-resonant two-photon (N2P) schemes .28,29 The non-resonant two-photon PFI-PE scheme is especially attractive because it only requires a tunable dye laser in the UV range, which is readily available to most modern laboratories . For specific molecular species with IE values below 12 eV, the N2P-PFI-PE scheme is a useful method for highresolution photoelectron measurements. Since the N2P process requires considerable laser fluences, the occurrence of dissociation and multiphoton ionization processes can cause complications in N2P-PFI studies . Significant fragmentation of parent photoions due to absorption of additional photons has been shown to prevent the measurement of the p...

show abstract

“…The potential energy curves for the neutral molecule and molecular ions were found in Refs. [32][33][34][35][36]. As for the nitrogen molecule, we plot the classically calculated traces on top of the experimental spectra for the O 2+ + O 2+ channel.…”

Section: B Oxygenmentioning

confidence: 99%

Time-resolved Coulomb-explosion imaging of nuclear wave-packet dynamics induced in diatomic molecules by intense few-cycle laser pulses

et al. 2011

View full text Add to dashboard Cite

We studied the nuclear dynamics in diatomic molecules (N 2 , O 2 , and CO) following their interaction with intense near-IR few-cycle laser pulses. Using Coulomb-explosion imaging in combination with the pump-probe approach, we mapped dissociation pathways of those molecules and their molecular ions. We identified all symmetric and asymmetric breakup channels for molecular ions up to N 5+ 2 , O 4+ 2 , and CO 4+ . For each of those channels we measured the kinetic energy release (KER) spectra as a function of delay between the pump and probe pulses. For both N 2 and O 2 the asymmetric (3,1) channel is only observed for short (<20 fs) delays and completely disappears after that. We interpret this observation as a signature of electron localization taking place in dissociating molecular tri-cations when their internuclear separation reaches about 2.5 times the equilibrium bond length. This is a direct confirmation that electron localization plays an essential role in the universal mechanism of enhanced ionization in homonuclear diatomic molecules. Using classical and quantum mechanical simulations of the time-dependent KER spectra, we identify the pathways and intermediate states involved in the laser-induced dissociation of those molecules.

show abstract

Configuration interaction calculations of low-lying electronic states of O2,O2+, and O22+

Cited by 176 publications

References 37 publications

High resolution threshold photoelectron spectrum of oxygen in the 12–19 eV region

High resolution threshold photoelectron spectrum of oxygen in the 12–19 eV region

Advances in Photoionization and Photoelectron Studies Using Third Generation Synchrotron Radiation and Uv/Vuv Lasers

Time-resolved Coulomb-explosion imaging of nuclear wave-packet dynamics induced in diatomic molecules by intense few-cycle laser pulses

Contact Info

Product

Resources

About