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Interconversion Energy Barrier (interconversion + energy_barrier)

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Chemistry100%

Selected Abstracts

DFT study and NBO analysis of the mutual interconversion of cumulene compounds

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 5 2007
Davood Nori-Shargh
Abstract The B3LYP/6-31G* method was used to investigate the configurational properties of allene (1,2-propadiene) (1), 1,2,3-butatriene (2), 1,2,3,4-pentateriene (3), 1,2,3,4,5-hexapentaene (4), 1,2,3,4,5,6-heptahexaene (5), 1,2,3,4,5,6,7-octaheptaene (6), 1,2,3,4,5,6,7,8-nonaoctaene (7), and 1,2,3,4,5,6,7,8,9-decanonaene (9). The calculations at the B3LYP/6-31G* level of theory showed that the mutual interconversion energy barrier in compounds 1,8 are: 209.73, 131.77, 120.34, 85.00, 80.91, 62.19, 55.56, and 46.83,kJ,mol,1, respectively. The results showed that the difference between the average CC double bond lengths () values in cumulene compounds 1 and 2, is larger than those between 7 and 8, which suggest that with large n (number of carbon atoms in cumulene chain), the values approach a limiting value. Accordingly, based on the plotted data, the extrapolation to n,=,,, gives nearly the same limiting (i. e., ). Also, NBO results revealed that the sum of , -bond occupancies, , decrease from 1 to 8, and inversely, the sum of , -antibonding orbital occupancies, , increase from compound 1 to compound 8. The decrease of values for compounds 1,8, is found to follow the same trend as the barrier heights of mutual interconversion in compounds 1,8, while the decrease of the barrier height of mutual interconversion in compounds 1,8 is found to follow the opposite trend as the increase in the number of carbon atom. Accordingly, besides the previously reported allylic resonant stabilization effect in the transition state structures, the results reveal that the values, , ,(EHOMO,,,ELUMO), and the C atom number could be considered as significant criteria for the mutual interconversion in cumulene compounds 1,8. This work reports also useful predictive linear relationships between mutual interconversion energy barriers () in cumulene compounds and the following four parameters: , , ,(EHOMO,,,ELUMO), and CNumber. Copyright © 2007 John Wiley & Sons, Ltd. [source]

Determination of the 2,3-pentadienedioic acid enantiomer interconversion energy barrier 1.

JOURNAL OF SEPARATION SCIENCE, JSS, Issue 15 2006
Classical kinetic approach
Abstract A classical kinetic method was used to determine the energy barrier for the interconversion of 2,3-pentadienedioic acid enantiomers. Each individual enantiomer was isolated by collecting the appropriate peaks from the HPLC enantiomeric separation, of racemic 2,3-pentadienedioic acid. The isolated enantiomers were racemized at 22°C using various interconversion times. The ratio of enantiomers in each reaction solution was determined by HPLC at 22°C. The corresponding peak areas of the enantiomers and the interconversion times obtained from the HPLC chromatograms were used to calculate both the interconversion rate constants describing (+) , (,) and (,) , (+) interconversions as well as the energy barriers. It was confirmed that the interconversion of 2,3-pentadienedioic acid enantiomers is a first-order kinetic reaction. Both semiempirical and ab initio methods were used to explore the mechanism of the interconversion of 2,3-pentadienedioic acid enantiomers, and to calculate the interconversion energy barrier. Comparison of the interconversion energy barriers found by the ab initio method (,G# = 110.7 kJ/mol) and by classical kinetics in the mobile phase solution at 22°C (,Gapp = 93.9 ± 0.2 kJ/mol) shows a difference which may be attributed to the different conditions assumed in the theoretical calculation (i. e., a gaseous state) and the actual experimental conditions (i. e., liquid solution) and a possible catalytic effect of the solution composition. [source]

DFT study and NBO analysis of the mutual interconversion of cumulene compounds

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 5 2007
Davood Nori-Shargh
Abstract The B3LYP/6-31G* method was used to investigate the configurational properties of allene (1,2-propadiene) (1), 1,2,3-butatriene (2), 1,2,3,4-pentateriene (3), 1,2,3,4,5-hexapentaene (4), 1,2,3,4,5,6-heptahexaene (5), 1,2,3,4,5,6,7-octaheptaene (6), 1,2,3,4,5,6,7,8-nonaoctaene (7), and 1,2,3,4,5,6,7,8,9-decanonaene (9). The calculations at the B3LYP/6-31G* level of theory showed that the mutual interconversion energy barrier in compounds 1,8 are: 209.73, 131.77, 120.34, 85.00, 80.91, 62.19, 55.56, and 46.83,kJ,mol,1, respectively. The results showed that the difference between the average CC double bond lengths () values in cumulene compounds 1 and 2, is larger than those between 7 and 8, which suggest that with large n (number of carbon atoms in cumulene chain), the values approach a limiting value. Accordingly, based on the plotted data, the extrapolation to n,=,,, gives nearly the same limiting (i. e., ). Also, NBO results revealed that the sum of , -bond occupancies, , decrease from 1 to 8, and inversely, the sum of , -antibonding orbital occupancies, , increase from compound 1 to compound 8. The decrease of values for compounds 1,8, is found to follow the same trend as the barrier heights of mutual interconversion in compounds 1,8, while the decrease of the barrier height of mutual interconversion in compounds 1,8 is found to follow the opposite trend as the increase in the number of carbon atom. Accordingly, besides the previously reported allylic resonant stabilization effect in the transition state structures, the results reveal that the values, , ,(EHOMO,,,ELUMO), and the C atom number could be considered as significant criteria for the mutual interconversion in cumulene compounds 1,8. This work reports also useful predictive linear relationships between mutual interconversion energy barriers () in cumulene compounds and the following four parameters: , , ,(EHOMO,,,ELUMO), and CNumber. Copyright © 2007 John Wiley & Sons, Ltd. [source]

Determination of the 2,3-pentadienedioic acid enantiomer interconversion energy barrier 1.

JOURNAL OF SEPARATION SCIENCE, JSS, Issue 15 2006
Classical kinetic approach
Abstract A classical kinetic method was used to determine the energy barrier for the interconversion of 2,3-pentadienedioic acid enantiomers. Each individual enantiomer was isolated by collecting the appropriate peaks from the HPLC enantiomeric separation, of racemic 2,3-pentadienedioic acid. The isolated enantiomers were racemized at 22°C using various interconversion times. The ratio of enantiomers in each reaction solution was determined by HPLC at 22°C. The corresponding peak areas of the enantiomers and the interconversion times obtained from the HPLC chromatograms were used to calculate both the interconversion rate constants describing (+) , (,) and (,) , (+) interconversions as well as the energy barriers. It was confirmed that the interconversion of 2,3-pentadienedioic acid enantiomers is a first-order kinetic reaction. Both semiempirical and ab initio methods were used to explore the mechanism of the interconversion of 2,3-pentadienedioic acid enantiomers, and to calculate the interconversion energy barrier. Comparison of the interconversion energy barriers found by the ab initio method (,G# = 110.7 kJ/mol) and by classical kinetics in the mobile phase solution at 22°C (,Gapp = 93.9 ± 0.2 kJ/mol) shows a difference which may be attributed to the different conditions assumed in the theoretical calculation (i. e., a gaseous state) and the actual experimental conditions (i. e., liquid solution) and a possible catalytic effect of the solution composition. [source]