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A combined theoreti...
A combined theoretical and experimental study of the ionic states of iodopentafluorobenzene
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- Palmer, Michael H. (författare)
- Univ Edinburgh, Sch Chem, Joseph Black Bldg,David Brewster Rd, Edinburgh EH9 3FJ, Midlothian, Scotland.
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- Coreno, Marcello (författare)
- CNR IMIP, Lab Elettra, Trieste, Italy.
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- de Simone, Monica (författare)
- CNR IOM, Lab TASC, Trieste, Italy.
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- Hoffmann, Soren Vronning (författare)
- Aarhus Univ, Dept Phys & Astron, ISA, Ny Munkegade 120, DK-8000 Aarhus C, Denmark.
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- Jones, Nykola C. (författare)
- Aarhus Univ, Dept Phys & Astron, ISA, Ny Munkegade 120, DK-8000 Aarhus C, Denmark.
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- Grazioli, Cesare (författare)
- CNR IMIP, Lab Elettra, Trieste, Italy.;Univ Trieste, Dept Chem & Pharmaceut Sci, Trieste, Italy.
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- Peterson, Kirk A. (författare)
- Washington State Univ, Dept Chem, Pullman, WA 99164 USA.
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- Baiardi, Alberto (författare)
- Scuola Normale Super Pisa, Piazza Cavalieri 7, I-56126 Pisa, Italy.
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- Zhang, Teng (författare)
- Uppsala universitet,Molekyl- och kondenserade materiens fysik
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- Biczysko, Malgorzata (författare)
- Shanghai Univ, Coll Sci, Int Ctr Quantum & Mol Struct, 99 Shangda Rd, Shanghai 200444, Peoples R China.
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Univ Edinburgh, Sch Chem, Joseph Black Bldg,David Brewster Rd, Edinburgh EH9 3FJ, Midlothian, Scotland CNR IMIP, Lab Elettra, Trieste, Italy. (creator_code:org_t)
- 2017-02-22
- 2017
- Engelska.
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Ingår i: Journal of Chemical Physics. - : American Institute of Physics (AIP). - 0021-9606 .- 1089-7690. ; 146:8
- Relaterad länk:
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https://pure.au.dk/w...
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Ämnesord
Stäng
- A new synchrotron radiation photoelectron spectral (PES) study of iodopentafluorobenzene, together with a theoretical analysis of the spectrum, where Franck-Condon factors are discussed, gives detailed insight into the ionization processes, and this exposes the need for a reinvestigation of the vacuum ultraviolet spectral (VUV) assignments. We have calculated adiabatic ionization energies (AIEs) for several ionic states, using the equation-of-motion coupled cluster method for ionic states combined with multi-configuration self-consistent field calculation study. The AIE sequence is: (XB1)-B-2 < A(2)A(2) < (BB2)-B-2 < C2(2)B(1) < D(2)A(1) < E3(2)B(1). This symmetry sequence has a major impact on previous VUV spectral assignments, which now appear to be to optically forbidden states. Changes in the equilibrium structures for these ionic states are relatively small, but a significant decrease and increase in the C-I bond length relative to the X(1)A(1) structure occurs for the (XB1)-B-2 and (CB1)-B-2 states, respectively. The PES shows major vibrational overlaps between pairs of ionic states, X with A, and A with B. The result of these overlaps is the loss of vibrational structure and considerable broadening of the higher energy PES state. Although the baseline is nearly re-established between the A and B states, where the two bands are nearly separate, the B state is also broadened by the A state. Only the C ionic state, which shows the most highly developed vibrational structure, can be regarded as free from vibrational coupling to a neighbor state. The Franck-Condon analysis of the PES bands X, A, B, and C is described in detail; the apparent simplicity of some of these bands is illusory, since almost all the observed peaks arise from super-position of several calculated vibrational states. The experimental AIE of the A state, which is submerged under the X state envelope, has been determined by the subtraction of the calculated X state envelope from the observed PES spectrum. The overlap of these PES bands and the apparent closeness of the potential energy curves describing them have been investigated, using the state-averaged, complete active space self-consistent field method. We have identified two structures, one where the potential energy curves for the X and A states cross and another for the A and B states. At these two conical intersections (ConInts), there is zero-energy difference within each pair of states. Although similar in energy, the ConInt for the crossing of the X with A states, and that for the A with B states, shows that the open-shell occupancies correspond to the 4 lowest AIE states, and all four states that are quite different from each other. Published by AIP Publishing.
Ämnesord
- NATURVETENSKAP -- Kemi -- Fysikalisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Physical Chemistry (hsv//eng)
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Palmer, Michael ...
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Coreno, Marcello
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de Simone, Monic ...
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Hoffmann, Soren ...
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Jones, Nykola C.
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Grazioli, Cesare
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Peterson, Kirk A ...
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Baiardi, Alberto
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Zhang, Teng
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Biczysko, Malgor ...
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Journal of Chemi ...
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Uppsala universitet