Localized-density-matrix calculation of circular dichroism spectrum of optically active molecule

Liang, WanZhen; Yokojima, Satoshi; Chen, Guanhua

doi:10.1016/s0301-0104(03)00019-3

Cited by 5 publications

(2 citation statements)

References 50 publications

(61 reference statements)

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“…The Cobalt(II)tris( there are issues tied to their use in finite basis sets. 52,[59][60][61] Indeed, the dipole-length representation gives origin-dependent rotatory strengths, which is not the case for the dipolevelocity form. This latter form, however, gives rotatory strengths which are sensitive to the quality of the wave functions.…”

Section: Computational and Experimental Detailsmentioning

confidence: 99%

“…The electric dipole moment operator is given in the dipole-length form by μ = − r , and in the dipole-velocity form, its matrix elements read μ ij = −(1/ E ij )∇ ij . The two representations are equivalent in a complete basis set, but there are issues tied to their use in finite basis sets. ,− Indeed, the dipole-length representation gives origin-dependent rotatory strengths, which is not the case for the dipole-velocity form. This latter form, however, gives rotatory strengths which are sensitive to the quality of the wave functions.…”

Section: Computational and Experimental Detailsmentioning

confidence: 99%

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Density-Functional Theory Investigation of the Geometric, Energetic, and Optical Properties of the Cobalt(II)tris(2,2‘-bipyridine) Complex in the High-Spin and the Jahn−Teller Active Low-Spin States

Vargas

Zerara

Krausz

et al. 2006

J. Chem. Theory Comput.

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State-of-the-art generalized gradient approximation (GGA) (PBE, OPBE, RPBE, OLYP, and HCTH), meta-GGA (VSXC and TPSS), and hybrid (B3LYP, B3LYP*, O3LYP, and PBE0) functionals are compared for the determination of the structure and the energetics of the D3 [Co(bpy)3](2+) complex in the (4)A2 and (4)E trigonal components of the high-spin (4)T1g([Formula: see text] [Formula: see text] ) state and in the low-spin (2)E state of octahedral (2)Eg([Formula: see text] [Formula: see text] ) parentage. Their comparison extends also to the investigation of the Jahn-Teller instability of the (2)E state through the characterization of the extrema of C2 symmetry of this spin state's potential energy surface. The results obtained for [Co(bpy)3](2+) in either spin manifold are very consistent among the functionals used and are in good agreement with available experimental data. The functionals, however, perform very differently with respect to the spin-state energetics because the calculated values of the high-spin/low-spin energy difference Δ[Formula: see text] vary between -3212 and 3919 cm(-)(1). Semilocal functionals tend to give too large Δ[Formula: see text] values and thus fail to correctly predict the high-spin state as the ground state of the isolated complex, while hybrid functionals tend to overestimate the stability of the high-spin state with respect to the low-spin state. Reliable results are, however, obtained with the OLYP, HCTH, B3LYP*, and O3LYP functionals which perform best for the description of the isolated complex. The optical properties of [Co(bpy)3](2+) in the two spin states are also analyzed on the basis of electronic excitation calculations performed within time-dependent density functional response theory. The calculated absorption and circular dichroism spectra agree well with experimental results.

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Section: Computational and Experimental Detailsmentioning

confidence: 99%

Section: Computational and Experimental Detailsmentioning

confidence: 99%

Density-Functional Theory Investigation of the Geometric, Energetic, and Optical Properties of the Cobalt(II)tris(2,2‘-bipyridine) Complex in the High-Spin and the Jahn−Teller Active Low-Spin States

Vargas

Zerara

Krausz

et al. 2006

J. Chem. Theory Comput.

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Interaction between polycyclic aromatic hydrocarbons and thymine (T)-base induces double-strand DNA distortion in different species

Liu,

Wu,

et al. 2024

Science of The Total Environment

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A new ultrafast technique for measuring the terahertz dynamics of chiral molecules: The theory of optical heterodyne-detected Raman-induced Kerr optical activity

Wynne

2005

The Journal of Chemical Physics

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Optical heterodyne-detected Raman-induced Kerr optical activity (OHD-RIKOA) is a nonresonant ultrafast chiroptical technique for measuring the terahertz-frequency Raman spectrum of chirally active modes in liquids, solutions, and glasses of chiral molecules. OHD-RIKOA has the potential to provide much more information on the structure of molecules and the symmetries of librational and vibrational modes than the well-known nonchirally sensitive technique optical heterodyne-detected Raman-induced Kerr-effect spectroscopy (OHD-RIKES). The theory of OHD-RIKOA is presented and possible practical ways of performing the experiments are analyzed.

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Localized-density-matrix calculation of circular dichroism spectrum of optically active molecule

Cited by 5 publications

References 50 publications

Density-Functional Theory Investigation of the Geometric, Energetic, and Optical Properties of the Cobalt(II)tris(2,2‘-bipyridine) Complex in the High-Spin and the Jahn−Teller Active Low-Spin States

Density-Functional Theory Investigation of the Geometric, Energetic, and Optical Properties of the Cobalt(II)tris(2,2‘-bipyridine) Complex in the High-Spin and the Jahn−Teller Active Low-Spin States

Interaction between polycyclic aromatic hydrocarbons and thymine (T)-base induces double-strand DNA distortion in different species

A new ultrafast technique for measuring the terahertz dynamics of chiral molecules: The theory of optical heterodyne-detected Raman-induced Kerr optical activity

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