Additivity of electron correlation energy and the ab initio MO calculation of (0-0) S 1←S 0 transition energies

Polychlorinated dibenzofurans

Tomoko Imasaka, Shoji Hirokawa

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The energies of the S 0 and S 1 states of polychlorinated dibenzofurans (PCDFs) were calculated using the Hartree-Fock (HF) and configuration interaction-singles (CIS) methods. We can obtain the (0-0) transition energies of PCDFs with good accuracy if the energies calculated using the HF and CIS methods are adjusted to take the electron correlation energy into account. The correlation energy of the S 0 state was calculated using the Møller-Plesset correlation correction truncated at the second order (MP2), and that of the S 1 state was determined using experimental data. The correlation energies for both S 0 and S 1 states were expressed as the sum of the contributions arising from dibenzofuran (DF) and substituted chlorine atoms. The energy of the ground state calculated using the additivity approximation was in good agreement with the energy given directly by the MP2 method. The (0-0) S 1←S 0 transition energies corrected for electron correlation energy agreed well with the available experimental data. The approach proposed in this paper may be useful for the estimation of the electronic transition energy for large aromatic molecules.

Original languageEnglish
Pages (from-to)19-23
Number of pages5
JournalJournal of Molecular Structure: THEOCHEM
Volume710
Issue number1-3
DOIs
Publication statusPublished - Nov 26 2004

Fingerprint

Electron correlations
Electrons
Chlorine
Electron transitions
Ground state
electrons
Atoms
Molecules
energy
configuration interaction
Polychlorinated Dibenzofurans
chlorine
dibenzofuran

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

@article{da0335a1130b4c1f92f15cd0e359faf7,
title = "Additivity of electron correlation energy and the ab initio MO calculation of (0-0) S 1←S 0 transition energies: Polychlorinated dibenzofurans",
abstract = "The energies of the S 0 and S 1 states of polychlorinated dibenzofurans (PCDFs) were calculated using the Hartree-Fock (HF) and configuration interaction-singles (CIS) methods. We can obtain the (0-0) transition energies of PCDFs with good accuracy if the energies calculated using the HF and CIS methods are adjusted to take the electron correlation energy into account. The correlation energy of the S 0 state was calculated using the M{\o}ller-Plesset correlation correction truncated at the second order (MP2), and that of the S 1 state was determined using experimental data. The correlation energies for both S 0 and S 1 states were expressed as the sum of the contributions arising from dibenzofuran (DF) and substituted chlorine atoms. The energy of the ground state calculated using the additivity approximation was in good agreement with the energy given directly by the MP2 method. The (0-0) S 1←S 0 transition energies corrected for electron correlation energy agreed well with the available experimental data. The approach proposed in this paper may be useful for the estimation of the electronic transition energy for large aromatic molecules.",
author = "Tomoko Imasaka and Shoji Hirokawa",
year = "2004",
month = "11",
day = "26",
doi = "10.1016/j.theochem.2004.08.003",
language = "English",
volume = "710",
pages = "19--23",
journal = "Computational and Theoretical Chemistry",
issn = "2210-271X",
publisher = "Elsevier BV",
number = "1-3",

}

TY - JOUR

T1 - Additivity of electron correlation energy and the ab initio MO calculation of (0-0) S 1←S 0 transition energies

T2 - Polychlorinated dibenzofurans

AU - Imasaka, Tomoko

AU - Hirokawa, Shoji

PY - 2004/11/26

Y1 - 2004/11/26

N2 - The energies of the S 0 and S 1 states of polychlorinated dibenzofurans (PCDFs) were calculated using the Hartree-Fock (HF) and configuration interaction-singles (CIS) methods. We can obtain the (0-0) transition energies of PCDFs with good accuracy if the energies calculated using the HF and CIS methods are adjusted to take the electron correlation energy into account. The correlation energy of the S 0 state was calculated using the Møller-Plesset correlation correction truncated at the second order (MP2), and that of the S 1 state was determined using experimental data. The correlation energies for both S 0 and S 1 states were expressed as the sum of the contributions arising from dibenzofuran (DF) and substituted chlorine atoms. The energy of the ground state calculated using the additivity approximation was in good agreement with the energy given directly by the MP2 method. The (0-0) S 1←S 0 transition energies corrected for electron correlation energy agreed well with the available experimental data. The approach proposed in this paper may be useful for the estimation of the electronic transition energy for large aromatic molecules.

AB - The energies of the S 0 and S 1 states of polychlorinated dibenzofurans (PCDFs) were calculated using the Hartree-Fock (HF) and configuration interaction-singles (CIS) methods. We can obtain the (0-0) transition energies of PCDFs with good accuracy if the energies calculated using the HF and CIS methods are adjusted to take the electron correlation energy into account. The correlation energy of the S 0 state was calculated using the Møller-Plesset correlation correction truncated at the second order (MP2), and that of the S 1 state was determined using experimental data. The correlation energies for both S 0 and S 1 states were expressed as the sum of the contributions arising from dibenzofuran (DF) and substituted chlorine atoms. The energy of the ground state calculated using the additivity approximation was in good agreement with the energy given directly by the MP2 method. The (0-0) S 1←S 0 transition energies corrected for electron correlation energy agreed well with the available experimental data. The approach proposed in this paper may be useful for the estimation of the electronic transition energy for large aromatic molecules.

UR - http://www.scopus.com/inward/record.url?scp=9644283094&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=9644283094&partnerID=8YFLogxK

U2 - 10.1016/j.theochem.2004.08.003

DO - 10.1016/j.theochem.2004.08.003

M3 - Article

VL - 710

SP - 19

EP - 23

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

SN - 2210-271X

IS - 1-3

ER -