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Title: Anharmonic modeling of the conformation-specific IR spectra of ethyl, n -propyl, and n -butylbenzene

Authors:
 [1]; ORCiD logo [2];  [2]; ORCiD logo [2];  [2];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemistry and Theoretical Chemistry Institute, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA
  2. Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1257004
Grant/Contract Number:
DEFG02-96ER14656
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 22; Related Information: CHORUS Timestamp: 2018-02-14 23:40:44; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

Citation Formats

Tabor, Daniel P., Hewett, Daniel M., Bocklitz, Sebastian, Korn, Joseph A., Tomaine, Anthony J., Ghosh, Arun K., Zwier, Timothy S., and Sibert, III, Edwin L.. Anharmonic modeling of the conformation-specific IR spectra of ethyl, n -propyl, and n -butylbenzene. United States: N. p., 2016. Web. doi:10.1063/1.4953181.
Tabor, Daniel P., Hewett, Daniel M., Bocklitz, Sebastian, Korn, Joseph A., Tomaine, Anthony J., Ghosh, Arun K., Zwier, Timothy S., & Sibert, III, Edwin L.. Anharmonic modeling of the conformation-specific IR spectra of ethyl, n -propyl, and n -butylbenzene. United States. doi:10.1063/1.4953181.
Tabor, Daniel P., Hewett, Daniel M., Bocklitz, Sebastian, Korn, Joseph A., Tomaine, Anthony J., Ghosh, Arun K., Zwier, Timothy S., and Sibert, III, Edwin L.. 2016. "Anharmonic modeling of the conformation-specific IR spectra of ethyl, n -propyl, and n -butylbenzene". United States. doi:10.1063/1.4953181.
@article{osti_1257004,
title = {Anharmonic modeling of the conformation-specific IR spectra of ethyl, n -propyl, and n -butylbenzene},
author = {Tabor, Daniel P. and Hewett, Daniel M. and Bocklitz, Sebastian and Korn, Joseph A. and Tomaine, Anthony J. and Ghosh, Arun K. and Zwier, Timothy S. and Sibert, III, Edwin L.},
abstractNote = {},
doi = {10.1063/1.4953181},
journal = {Journal of Chemical Physics},
number = 22,
volume = 144,
place = {United States},
year = 2016,
month = 6
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1063/1.4953181

Citation Metrics:
Cited by: 9works
Citation information provided by
Web of Science

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  • The heat capacities from 12 to 370/sup 0/K., heats of fusion, triple points, and purities of n-propyl-benzene and n-butylbenzene were measured in an adiabatic calorimeter. Both compounds exhibited monotropism with the metastable crystals melting 2.02/sup 0/ below the stable crystals in the case of n-propylbenzene and 0.16/sup 0/ below the stable crystals in the case of n-butyl-benzene. From the calorimetrically measured data the thermodynamic functions (G/sub s/ - H/sup 0//sub 0/)/T, (H/sub s/ - H/sup 0//sub 0/)/T, H/sub s/ - H/sup 0//sub 0/, S/sub s/, and C/sub s/ were calculated at selected temperatures for each compound for both the metastablemore » and stable crystals and the liquid phase. For each compound, the entropies at 298.15/sup 0/K in the liquid state calculated by metastable and by stable paths agreed within experimental error, providing another check of the third law of thermodynamics. The entropy increment obtained between n-propyl- and n-butylbenzene is about 0.25 e.u greater than the constant entropy increment for the normal paraffins from C/sub 5/ to C/sub 18/ in both the liquid and ideal gas states. This slightly larger increment from n-propyl to n-butyl substitution has been noticed earlier in monoalkyl-substituted cyclopentanes and cyclohexanes. From incomplete measurements on n-decylbenzene, values of the heat of melting and triple point temperature were obtained. Estimates of the entropies of n-decylbenzene at 298.15/sup 0/K in the liquid and ideal gas states were made.« less
  • Potential energy surfaces for rotation about the C(sp{sup 2}){single_bond}C(sp{sup 3}) bond are reported for acetamide, propanamide, 2-methylpropanamide, and 2,2-dimethylpropanamide at different levels of ab initio electronic structure theory with correlation effects included. In all cases, fully optimized geometries of rotational minima are consistent with gas phase electron diffraction data and crystal structure data. The experimental barrier height for methyl rotation in acetamide is reproduced to within 0.1 kcal/mol. This study yields a set of improved criteria for the construction of rotational potentials for the C{sub a}{single_bond}C bond which are used to obtain improved MM3 torsional parameters. In addition, the authorsmore » find that the use of higher levels of theory leads to significantly different results than those obtained in prior Hartree-Fock studies on acetamide and 2-methylpropanamide.« less