No data available.

Please log in to see this content.

You have no subscription access to this content.

No metrics data to plot.

The attempt to load metrics for this article has failed.

The attempt to plot a graph for these metrics has failed.

*Ab initio* calculations on and low-lying cationic states of : Franck-Condon simulation of the UV photoelectron spectrum of

Rent:

Rent this article for

USD

10.1063/1.2202734

### Abstract

Geometry optimization calculations were carried out on the state of and the , , , , , and states of at the restricted-spin coupled-cluster single-double plus perturbative triple excitation [RCCSD(T)] level with basis sets of up to the augmented correlation-consistent polarized quintuple-zeta quality. Effects of core electron correlation, basis set extension to the complete basis set limit, and relativistic contributions on computed minimum-energy geometrical parameters and/or relative electronic energies were also investigated. RCCSD(T) potential energy functions (PEFs) were calculated for the state of and the low-lying states of listed above employing the basis set. Anharmonic vibrational wave functions of these neutral and cationic states of , and Franck-Condon (FC) factors of the lowest four one-electron allowed neutral photoionizations were computed employing the PEFs. Calculated FC factors with allowance for the Duschinsky rotation and anharmonicity were used to simulate the first four photoelectron (PE) bands of . The agreement between simulated and observed PE spectra reported by Colton *et al.* [J. Electron Spectrosc. Relat. Phenom.3, 345 (1974)] and Solouki *et al.* [Chem. Phys. Lett.26, 20 (1974)] is excellent. However, our FC spectral simulations indicate that the first observed vibrational component in the first PE band of is a “hot” band arising from the ionization. Consequently, the experimental adiabatic ionization energy of is revised to , in excellent agreement with results obtained from state-of-the-art *ab initio* calculations in this work.

© 2006 American Institute of Physics

Received 09 March 2006
Accepted 13 April 2006
Published online 08 September 2006

Acknowledgments: Financial support from the Research Grant Council (RGC) of the Hong Kong Special Administrative Region (HKSAR, Grant Nos. AoE/B-10/1 PolyU and PolyU 5003/04P) and provision of computational resources from the EPSRC (UK) National Service for Computational Chemistry Software are acknowledged.

Article outline:

I. INTRODUCTION

II. THEORETICAL CONSIDERATIONS AND COMPUTATIONAL DETAILS

A. *Ab initio* calculations

III. POTENTIAL ENERGY FUNCTIONS, ANHARMONIC VIBRATIONAL WAVE FUNCTIONS, AND FRANCK-CONDON FACTOR CALCULATIONS

IV. RESULTS AND DISCUSSIONS

A. The one-electron forbidden and states of

B. Optimized geometrical parameters and computed vibrational frequencies

C. Relative electronic energies: Vertical and adiabatic ionization energies

D. Spectral simulations: First PE band of

E. Spectral simulations: Higher IE bands of

V. CONCLUDING REMARKS

/content/aip/journal/jcp/125/10/10.1063/1.2202734

http://aip.metastore.ingenta.com/content/aip/journal/jcp/125/10/10.1063/1.2202734

Article metrics loading...

/content/aip/journal/jcp/125/10/10.1063/1.2202734

2006-09-08

2014-04-24

Full text loading...

### Most read this month

Article

content/aip/journal/jcp

Journal

5

3

Commenting has been disabled for this content