Interpretation of the vacuum ultraviolet photoabsorption spectrum of iodobenzene by ab initio computations
- School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, Scotland (United Kingdom)
- CNR-ISM, Montelibretti, c/o Laboratorio Elettra, Trieste (Italy)
- CNR-IOM Laboratorio TASC, Trieste (Italy)
Identification of many Rydberg states in iodobenzene, especially from the first and fourth ionization energies (IE{sub 1} and IE{sub 4}, X{sup 2}B{sub 1} and C{sup 2}B{sub 1}), has become possible using a new ultraviolet (UV) and vacuum-ultraviolet (VUV) absorption spectrum, in the region 29 000-87 000 cm{sup −1} (3.60-10.79 eV), measured at room temperature with synchrotron radiation. A few Rydberg states based on IE{sub 2} (A{sup 2}A{sub 2}) were found, but those based on IE{sub 3} (B{sup 2}B{sub 2}) are undetectable. The almost complete absence of observable Rydberg states relating to IE{sub 2} and IE{sub 3} (A{sup 2}A{sub 2} and B{sup 2}B{sub 2}, respectively) is attributed to them being coupled to the near-continuum, high-energy region of Rydberg series converging on IE{sub 1}. Theoretical studies of the UV and VUV spectra used both time-dependent density functional (TDDFT) and multi-reference multi-root doubles and singles-configuration interaction methods. The theoretical adiabatic excitation energies, and their corresponding vibrational profiles, gave a satisfactory interpretation of the experimental results. The calculations indicate that the UV onset contains both 1{sup 1}B{sub 1} and 1{sup 1}B{sub 2} states with very low oscillator strength, while the 2{sup 1}B{sub 1} state was found to lie under the lowest ππ{sup ∗} 1{sup 1}A{sub 1} state. All three of these {sup 1}B{sub 1} and {sup 1}B{sub 2} states are excitations into low-lying σ{sup ∗} orbitals. The strongest VUV band near 7 eV contains two very strong ππ{sup ∗} valence states, together with other weak contributors. The lowest Rydberg 4b{sub 1}6s state (3{sup 1}B{sub 1}) is very evident as a sharp multiplet near 6 eV; its position and vibrational structure are well reproduced by the TDDFT results.
- OSTI ID:
- 22415606
- Journal Information:
- Journal of Chemical Physics, Vol. 142, Issue 13; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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