Assignment of absolute configurations of chiral phospholene oxides by UV/CD spectroscopy using TD-DFT quantum chemical calculations and singular value decomposition approach for the analysis of the spectra

Zsuzsa A. Mayer, M. Kállay, M. Kubinyi, G. Keglevich, Viktória Ujj, E. Fogassy

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The UV absorption and circular dichroism (CD) spectra of P-chiral 1-substituted-3-methyl-3-phospholene 1-oxides were analyzed on the basis of quantum chemical calculations aiming at the assignment of the absolute configurations of the molecules. Geometry optimization and determination of the most stable conformers were performed using density functional theory (DFT). The energies, oscillatory strengths and rotatory strengths of the singlet electronic transitions have been determined by time-dependent DFT (TD-DFT) method. For the qualitative description of the excitation patterns, the various natural molecular orbitals characteristic for the excitation process have been determined by using a singular value decomposition (SVD) algorithm recently proposed by Mayer [I. Mayer, Chem. Phys. Lett. 437 (2007) 284].

Original languageEnglish
Pages (from-to)94-99
Number of pages6
JournalJournal of Molecular Structure: THEOCHEM
Volume906
Issue number1-3
DOIs
Publication statusPublished - Jul 30 2009

Fingerprint

Circular dichroism spectroscopy
Singular value decomposition
Circular Dichroism
Ultraviolet spectroscopy
Discrete Fourier transforms
Oxides
dichroism
Density functional theory
Spectrum Analysis
density functional theory
decomposition
oxides
Molecular orbitals
configurations
spectroscopy
excitation
molecular orbitals
Molecules
optimization
Geometry

Keywords

  • Absolute configuration
  • Chiral phosphorous compounds
  • Conformational analysis
  • DFT calculations
  • Simulation of CD spectra
  • SVD method

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Biochemistry
  • Condensed Matter Physics

Cite this

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title = "Assignment of absolute configurations of chiral phospholene oxides by UV/CD spectroscopy using TD-DFT quantum chemical calculations and singular value decomposition approach for the analysis of the spectra",
abstract = "The UV absorption and circular dichroism (CD) spectra of P-chiral 1-substituted-3-methyl-3-phospholene 1-oxides were analyzed on the basis of quantum chemical calculations aiming at the assignment of the absolute configurations of the molecules. Geometry optimization and determination of the most stable conformers were performed using density functional theory (DFT). The energies, oscillatory strengths and rotatory strengths of the singlet electronic transitions have been determined by time-dependent DFT (TD-DFT) method. For the qualitative description of the excitation patterns, the various natural molecular orbitals characteristic for the excitation process have been determined by using a singular value decomposition (SVD) algorithm recently proposed by Mayer [I. Mayer, Chem. Phys. Lett. 437 (2007) 284].",
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T1 - Assignment of absolute configurations of chiral phospholene oxides by UV/CD spectroscopy using TD-DFT quantum chemical calculations and singular value decomposition approach for the analysis of the spectra

AU - Mayer, Zsuzsa A.

AU - Kállay, M.

AU - Kubinyi, M.

AU - Keglevich, G.

AU - Ujj, Viktória

AU - Fogassy, E.

PY - 2009/7/30

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N2 - The UV absorption and circular dichroism (CD) spectra of P-chiral 1-substituted-3-methyl-3-phospholene 1-oxides were analyzed on the basis of quantum chemical calculations aiming at the assignment of the absolute configurations of the molecules. Geometry optimization and determination of the most stable conformers were performed using density functional theory (DFT). The energies, oscillatory strengths and rotatory strengths of the singlet electronic transitions have been determined by time-dependent DFT (TD-DFT) method. For the qualitative description of the excitation patterns, the various natural molecular orbitals characteristic for the excitation process have been determined by using a singular value decomposition (SVD) algorithm recently proposed by Mayer [I. Mayer, Chem. Phys. Lett. 437 (2007) 284].

AB - The UV absorption and circular dichroism (CD) spectra of P-chiral 1-substituted-3-methyl-3-phospholene 1-oxides were analyzed on the basis of quantum chemical calculations aiming at the assignment of the absolute configurations of the molecules. Geometry optimization and determination of the most stable conformers were performed using density functional theory (DFT). The energies, oscillatory strengths and rotatory strengths of the singlet electronic transitions have been determined by time-dependent DFT (TD-DFT) method. For the qualitative description of the excitation patterns, the various natural molecular orbitals characteristic for the excitation process have been determined by using a singular value decomposition (SVD) algorithm recently proposed by Mayer [I. Mayer, Chem. Phys. Lett. 437 (2007) 284].

KW - Absolute configuration

KW - Chiral phosphorous compounds

KW - Conformational analysis

KW - DFT calculations

KW - Simulation of CD spectra

KW - SVD method

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