TY - JOUR

T1 - Ab initio MO study on the S1 ← S0 origin transition energies of polychlorodibenzofurans (PCDFs)

AU - Imasaka, Tomoko

AU - Hirokawa, Shoji

AU - Imasaka, Totaro

PY - 2006/11/6

Y1 - 2006/11/6

N2 - The geometries and energies for the S0 and S1 states of dibenzofuran (DF) and all 135 PCDFs were obtained using Hartree-Fock (HF) and CI-Singles (CIS) methods. The transition energies determined from HF and CIS energies were corrected for electron correlation. If the electron correlation energies for the S0 and the S1 state are calculated using a second-order Møller-Plesset perturbation (MP2) and a perturbative correction to CIS (termed CIS(D)) method, the S1 ← S0 0-0 transition energies are given with an error of 15.4-22.6%. Electron correlation corrections to the transition energies were determined from a selected set of experimental transition energies on the assumption of the following additivity rule: the electron correlation energy of each state can be partitioned into contributions from the parent molecule and substituent chlorines. The transition energies after correction for electron correlation are in good agreement with available experimental data with an error of 0.2-3.5%. The validity of the additivity rule with respect to electron correlation energy is discussed in relation to the geometry of the molecule. The findings show that the additivity rule holds within an error of 0.4%. Vertical ionization potentials, which are useful in REMPI spectral studies, were calculated using Koopmans' theorem. The results confirmed that the S1 ← S0 origin transition energy is inversely proportional to the number of chlorine atoms nCl but the ionization potential is directly proportional to nCl.

AB - The geometries and energies for the S0 and S1 states of dibenzofuran (DF) and all 135 PCDFs were obtained using Hartree-Fock (HF) and CI-Singles (CIS) methods. The transition energies determined from HF and CIS energies were corrected for electron correlation. If the electron correlation energies for the S0 and the S1 state are calculated using a second-order Møller-Plesset perturbation (MP2) and a perturbative correction to CIS (termed CIS(D)) method, the S1 ← S0 0-0 transition energies are given with an error of 15.4-22.6%. Electron correlation corrections to the transition energies were determined from a selected set of experimental transition energies on the assumption of the following additivity rule: the electron correlation energy of each state can be partitioned into contributions from the parent molecule and substituent chlorines. The transition energies after correction for electron correlation are in good agreement with available experimental data with an error of 0.2-3.5%. The validity of the additivity rule with respect to electron correlation energy is discussed in relation to the geometry of the molecule. The findings show that the additivity rule holds within an error of 0.4%. Vertical ionization potentials, which are useful in REMPI spectral studies, were calculated using Koopmans' theorem. The results confirmed that the S1 ← S0 origin transition energy is inversely proportional to the number of chlorine atoms nCl but the ionization potential is directly proportional to nCl.

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U2 - 10.1016/j.theochem.2006.07.005

DO - 10.1016/j.theochem.2006.07.005

M3 - Article

AN - SCOPUS:33748440936

VL - 774

SP - 7

EP - 12

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

SN - 2210-271X

IS - 1-3

ER -