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The optical activity of carvone: A theoretical and experimental investigation
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10.1063/1.3693270
/content/aip/journal/jcp/136/11/10.1063/1.3693270
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/11/10.1063/1.3693270

Figures

Image of FIG. 1.
FIG. 1.

The six stable conformers of carvone.

Image of FIG. 2.
FIG. 2.

The ORD of S-(+)-carvone in 17 different solvents fit to a one parameter Drude model. For clarity some of the Drude model fits have been omitted but the parameters for those fits are included in the supplementary material.65

Image of FIG. 3.
FIG. 3.

Plot of data calculated using the Kamlet-Taft parameters found in this study versus the measured experimental optical rotation at 589 nm. The line represents perfect correlation between the experimental and calculated values.

Image of FIG. 4.
FIG. 4.

Representative CD (dashed line) and UV/visible (solid line) spectrum of (S)-carvone in cyclohexane.

Image of FIG. 5.
FIG. 5.

CD spectra of (S)-(+)-carvone in various solvents. The acetone and cyclopentanone data sets have large error below 315 nm and 340 nm, respectively, due to solvent absorption.

Image of FIG. 6.
FIG. 6.

Measured gas phase ECD of (S)-(+)-carvone in millidegrees of ellipticity.

Image of FIG. 7.
FIG. 7.

Computed ECD spectrum of (S)-(+)-carvone. (A) Plot of theoretical ECD calculated using populations from the G3 method and B3LYP/aDZ. (B) Comparison of theory and experimental CD of (S)-(+)-carvone in cyclohexane.

Tables

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Table I.

Computed relative energies and populations of the conformers of carvone.

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Table II.

Calculated optical rotation (deg dm−1 (g/ml)−1) of (S)-(+)-carvone using the PCM model. Both the structure and the optical rotation were computed using the aDZ basis set.

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Table III.

Measured ORD of (S)-(+)-carvone (deg dm−1 (g/ml)−1).

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Table IV.

Solvent parameters used in this study (Refs. 1 and 8, and 9).

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Table V.

Transition energies of the n → π* peaks and corresponding energy differences between adjacent peaks in the (R)-carvone ECD spectrum.

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Table VI.

Specific rotations (in deg dm−1 (g/ml)−1) of (R)-(−)-carvone at 589 nm computed using B3LYP and various basis sets with (〈[α] D 〉) and without ([α] D ) vibrational corrections from Table IX.

Generic image for table
Table VII.

Specific rotations (in deg dm−1 (g/ml)−1) at 589 nm computed using CC2 and various basis sets with (〈[α] D 〉) and without ([α] D ) vibrational corrections from Table IX.

Generic image for table
Table VIII.

Specific rotation (in deg dm−1 (g/ml)−1) of (R)- carvone at 589 nm computed using CCSD and the aDZ/DZ basis set with (〈[α] D 〉) and without ([α] D ) vibrational corrections from Table IX.

Generic image for table
Table IX.

Harmonic vibrational corrections (in deg dm−1 (g/ml)−1) to the specific rotation at 589 nm for each conformer of (R)-carvone.

Generic image for table
Table X.

Calculated optical rotation (deg dm−1 (g/ml)−1) of (S)-(+)-carvone using the PCM model. The ORD was calculated using structures optimized with B3LYP/aDZ and the relative population of each conformer was determined using the Gibbs free energy obtained from G3MP2 calculations.

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/content/aip/journal/jcp/136/11/10.1063/1.3693270
2012-03-20
2014-04-16
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: The optical activity of carvone: A theoretical and experimental investigation
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/11/10.1063/1.3693270
10.1063/1.3693270
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