Density functional theory calculations of optical rotation: Employment of ADZP and its comparison with other basis sets

Neto, A. Canal; Jorge, F.E.

doi:10.1002/chir.20343

Cited by 22 publications

(18 citation statements)

References 34 publications

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“…This was similar to the theoretical CD spectra obtained by the TDDFT method. 9,11,12,14 On the other hand, the CC method 15,18 gave, in general, a better agreement with the experimental CD spectra in both the shapes and the peak positions.…”

Section: Circular Dichroism (Cd)mentioning

confidence: 83%

Circular Dichroism and Absorption Spectroscopy for Three-Membered Ring Compounds Using Symmetry-Adapted Cluster-Configuration Interaction (SAC-CI) Method

Miyahara¹,

Hasegawa²,

Nakatsuji³

2009

Bulletin of the Chemical Society of Japan

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The singlet excited states of oxirane and thiirane derivatives, ethylene oxide, (R)-methyloxirane, (2S,3S)-dimethyloxirane, ethylene sulfide, (R)-methylthiirane, and (2S,3S)-dimethylthiirane, were calculated employing the symmetryadapted cluster (SAC)/SAC-configuration interaction (CI) method. The rotatory strengths of the CD spectra were calculated in the velocity form, which is gauge-origin independent. Both the ultraviolet (UV) spectra and the circular dichroism (CD) spectra obtained with the SAC-CI method were in good agreement with the experimental spectra. In oxirane derivatives, the low-lying excited states were composed of excitations from n and · orbitals to s, p, and d Rydberg orbitals. The excitation from the · orbital was especially important in (2S,3S)-dimethyloxirane because of the steric effect of the methyl substitutions. However, in thiirane derivatives, the excitations to the low-lying excited states were only from the n orbital.

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Section: Circular Dichroism (Cd)mentioning

confidence: 83%

Circular Dichroism and Absorption Spectroscopy for Three-Membered Ring Compounds Using Symmetry-Adapted Cluster-Configuration Interaction (SAC-CI) Method

Miyahara¹,

Hasegawa²,

Nakatsuji³

2009

Bulletin of the Chemical Society of Japan

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“…These sets were extended by Canal Neto et al [8] and Fantin et al [12] by augmenting the sets for H and Li-Ar with functions to more accurately describe the long range behavior of the wave functions. Next, the augmented XZP (AXZP, X ϭ D, T, and Q) sets [8,12] were used at the DFT and MP2 levels of theory to compute electric properties of N 2 , FH, H 2 O, and HCN [8,12] and optical rotations of 30 rigid chiral molecules [13,14]. For any property, one verified that the theoretical results were in good agreement with experimental data.…”

mentioning

confidence: 86%

“…Thus, there are some advantages of the former set over the latter ones, namely: Beyond the ADZP basis set can achieve accuracy comparable to specific sets generated to carry out electric property calculations, it can also be applied to study any property that is dependent on an accurate description of the long-range nature of the wave function (cf., Refs. [8,[12][13][14]). In addition, we have shown that for compounds like those studied here, ADZP along with DFT methods [BP86 (dipole moments) and B3LYP (polarizabilities)] form a reliable and unexpensive model for the prediction of electric properties.…”

Section: Polarizabilitymentioning

confidence: 98%

Basis set convergence of electric properties in HF and DFT calculations of nucleic acid bases

Campos

Jorge

2008

Int J of Quantum Chemistry

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ABSTRACT:Recently, a hierarchical sequence of augmented basis sets of double, triple, and quadruple zeta valence quality plus polarization functions (AXZP, X ϭ D, T, and Q) for the atoms from H to Ar were presented by Jorge et al. We report a systematic study of basis sets required to obtain accurate values of several electric properties for benzene, pyridine, the five common nucleic acid bases (uracil, cytosine, thymine, guanine, and adenine), and three related bases (fluorouracil, 5-methylcytosine, and hypoxanthine) at their full optimized geometries. Two methods were examined: Hartree-Fock (HF) and density functional theory (DFT). Including electron correlation decreases the magnitude of the dipole moment and increases the mean polarizability and also the polarizability anisotropy for every molecule. Calculated B3LYP/ADZP dipole moments and dipole polarizabilities show good agreement with both experimental and ab initio results based on second-order Mller-Plesset perturbation theory calculations. We have also showed that a basis set of double zeta quality is enough to obtain reliable and accurate electric property results for this kind of compounds.

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“…The results depend considerably on the exchange-correlation functional chosen. Even so, the TDDFT linear response formalism has been applied with success to the calculation of OR [8][9][10][11][12][13] and electronic circular dichroism (ECD) [14][15][16][17] of various compounds.…”

Section: Introductionmentioning

confidence: 99%

CAM‐B3LYP optical rotations at different wavelengths: Comparison with CCSD results

Jorge

Oliveira

Silva

2015

Int J of Quantum Chemistry

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A hierarchical sequence of basis sets along with one long‐range corrected functional (CAM‐B3LYP) were used to calculate electronic optical rotations (OR) at three wavelengths (355.0, 589.3, and 633.0 nm) of 14 rigid chiral molecules whose experimental values are available in the literature. As the results showed to be sensitive to the basis set quality, complete basis set limits were estimated. Special attention was given to five particularly difficult compounds. In these cases, one verifies that vibrational corrections (taken from the literature) must be added to the CAM‐B3LYP equilibrium OR to correct signs. In general, the complete basis set limits reported in this work are in good agreement with the experimental data and with those obtained at a higher level of theory. For some compounds, solvent effects are taken into account by means of the polarizable continuum model. For the solvated systems, the dependence between OR and cavity size is also examined. © 2015 Wiley Periodicals, Inc.

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Density functional theory calculations of optical rotation: Employment of ADZP and its comparison with other basis sets

Cited by 22 publications

References 34 publications

Circular Dichroism and Absorption Spectroscopy for Three-Membered Ring Compounds Using Symmetry-Adapted Cluster-Configuration Interaction (SAC-CI) Method

Circular Dichroism and Absorption Spectroscopy for Three-Membered Ring Compounds Using Symmetry-Adapted Cluster-Configuration Interaction (SAC-CI) Method

Basis set convergence of electric properties in HF and DFT calculations of nucleic acid bases

CAM‐B3LYP optical rotations at different wavelengths: Comparison with CCSD results

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