Quantumchemical (MNDO SCF/CI) calculations of the chiroptical properties of twisted conjugated diene and dione chromophores

M.C.A. Donkersloot, H.M. Buck

Research output: Contribution to journalArticleAcademicpeer-review

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Abstract

In this study the utility of wavefunctions, generated with the MNDO method is investigated for the computation of the oscillator strength and the rotational strength of molecules containing twisted conjugated diene and dione chromophores. In order to improve the quality of the excited-state wavefunctions, limited configuration interaction has been applied. For a-dienes (1,3-butadiene, 1,3-cyclohexadiene, 1,4- dimethylcyclohexa-2,4-diene) the method produces results which are comparable with earlier ab initio SCF/CI calculations. The results demonstrate that for these compounds the twisting of the a-diene fragment is the main factor determining the optical activity. On the other hand, for a-diones (glyoxal, bornane-2,3-dione) it is found that significant differences exist between the chiroptical properties of unsubstituted and substituted glyoxal, even if the twist angle of the a-dione fragment is kept unaltered. It appears that for the calculation of the chiroptical properties of such compounds it is essential to be able to treat relatively large molecular systems. It is suggested that the MNDO-based approach used offers a convenient tool for such calculations.
Original languageEnglish
Pages (from-to)347-364
Number of pages18
JournalJournal of Molecular Structure: THEOCHEM
Volume137
Issue number3-4
DOIs
Publication statusPublished - 1986

Fingerprint

Glyoxal
Dione
dienes
Chromophores
chromophores
self consistent fields
Optical Rotation
Wave functions
fragments
optical activity
twisting
butadiene
Excited states
oscillator strengths
configuration interaction
Molecules
excitation
molecules
1,3-cyclohexadiene
camphane

Cite this

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title = "Quantumchemical (MNDO SCF/CI) calculations of the chiroptical properties of twisted conjugated diene and dione chromophores",
abstract = "In this study the utility of wavefunctions, generated with the MNDO method is investigated for the computation of the oscillator strength and the rotational strength of molecules containing twisted conjugated diene and dione chromophores. In order to improve the quality of the excited-state wavefunctions, limited configuration interaction has been applied. For a-dienes (1,3-butadiene, 1,3-cyclohexadiene, 1,4- dimethylcyclohexa-2,4-diene) the method produces results which are comparable with earlier ab initio SCF/CI calculations. The results demonstrate that for these compounds the twisting of the a-diene fragment is the main factor determining the optical activity. On the other hand, for a-diones (glyoxal, bornane-2,3-dione) it is found that significant differences exist between the chiroptical properties of unsubstituted and substituted glyoxal, even if the twist angle of the a-dione fragment is kept unaltered. It appears that for the calculation of the chiroptical properties of such compounds it is essential to be able to treat relatively large molecular systems. It is suggested that the MNDO-based approach used offers a convenient tool for such calculations.",
author = "M.C.A. Donkersloot and H.M. Buck",
year = "1986",
doi = "10.1016/0166-1280(86)80129-4",
language = "English",
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pages = "347--364",
journal = "Journal of Molecular Structure: THEOCHEM",
issn = "0166-1280",
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Quantumchemical (MNDO SCF/CI) calculations of the chiroptical properties of twisted conjugated diene and dione chromophores. / Donkersloot, M.C.A.; Buck, H.M.

In: Journal of Molecular Structure: THEOCHEM, Vol. 137, No. 3-4, 1986, p. 347-364.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Quantumchemical (MNDO SCF/CI) calculations of the chiroptical properties of twisted conjugated diene and dione chromophores

AU - Donkersloot, M.C.A.

AU - Buck, H.M.

PY - 1986

Y1 - 1986

N2 - In this study the utility of wavefunctions, generated with the MNDO method is investigated for the computation of the oscillator strength and the rotational strength of molecules containing twisted conjugated diene and dione chromophores. In order to improve the quality of the excited-state wavefunctions, limited configuration interaction has been applied. For a-dienes (1,3-butadiene, 1,3-cyclohexadiene, 1,4- dimethylcyclohexa-2,4-diene) the method produces results which are comparable with earlier ab initio SCF/CI calculations. The results demonstrate that for these compounds the twisting of the a-diene fragment is the main factor determining the optical activity. On the other hand, for a-diones (glyoxal, bornane-2,3-dione) it is found that significant differences exist between the chiroptical properties of unsubstituted and substituted glyoxal, even if the twist angle of the a-dione fragment is kept unaltered. It appears that for the calculation of the chiroptical properties of such compounds it is essential to be able to treat relatively large molecular systems. It is suggested that the MNDO-based approach used offers a convenient tool for such calculations.

AB - In this study the utility of wavefunctions, generated with the MNDO method is investigated for the computation of the oscillator strength and the rotational strength of molecules containing twisted conjugated diene and dione chromophores. In order to improve the quality of the excited-state wavefunctions, limited configuration interaction has been applied. For a-dienes (1,3-butadiene, 1,3-cyclohexadiene, 1,4- dimethylcyclohexa-2,4-diene) the method produces results which are comparable with earlier ab initio SCF/CI calculations. The results demonstrate that for these compounds the twisting of the a-diene fragment is the main factor determining the optical activity. On the other hand, for a-diones (glyoxal, bornane-2,3-dione) it is found that significant differences exist between the chiroptical properties of unsubstituted and substituted glyoxal, even if the twist angle of the a-dione fragment is kept unaltered. It appears that for the calculation of the chiroptical properties of such compounds it is essential to be able to treat relatively large molecular systems. It is suggested that the MNDO-based approach used offers a convenient tool for such calculations.

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