Anharmonic modeling of the conformation-specific IR spectra of ethyl, n-propyl, and n-butylbenzene
Abstract
In this paper, conformation-specific UV-IR double resonance spectra are presented for ethyl, n-propyl, and n-butylbenzene. With the aid of a local mode Hamiltonian that includes the effects of stretch-scissor Fermi resonance, the spectra can be accurately modeled for specific conformers. These molecules allow for further development of a first principles method for calculating alkyl stretch spectra. Across all chain lengths, certain dihedral patterns impart particular spectral motifs at the quadratic level. However, the anharmonic contributions are consistent from molecule to molecule and conformer to conformer. This transferability of anharmonicities allows for the Hamiltonian to be constructed from only a harmonic frequency calculation, reducing the cost of the model. Finally, the phenyl ring alters the frequencies of the CH2 stretches by about 15 cm-1 compared to their n-alkane counterparts in trans configurations. Conformational changes in the chain can lead to shifts in frequency of up to 30 cm-1.
- Authors:
-
- Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry. Theoretical Chemistry Inst.
- Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Purdue Univ., West Lafayette, IN (United States); Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); German Research Foundation (DFG)
- OSTI Identifier:
- 1471526
- Alternate Identifier(s):
- OSTI ID: 1257004
- Grant/Contract Number:
- FG02-96ER14656; CHE-1213449; SU 121/6-1
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 144; Journal Issue: 22; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical compounds and components; Becke, three-parameter, Lee-Yang-Parr; Fermi resonance; electronic structure methods; chemical elements; organic compounds; electronic-structure theory; spectroscopy; correlation-consistent basis sets; conformational dynamics
Citation Formats
Tabor, Daniel P., Hewett, Daniel M., Bocklitz, Sebastian, Korn, Joseph A., Tomaine, Anthony J., Ghosh, Arun K., Zwier, Timothy S., and Sibert, 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, Edwin L. Anharmonic modeling of the conformation-specific IR spectra of ethyl, n-propyl, and n-butylbenzene. United States. https://doi.org/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, Edwin L. Tue .
"Anharmonic modeling of the conformation-specific IR spectra of ethyl, n-propyl, and n-butylbenzene". United States. https://doi.org/10.1063/1.4953181. https://www.osti.gov/servlets/purl/1471526.
@article{osti_1471526,
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, Edwin L.},
abstractNote = {In this paper, conformation-specific UV-IR double resonance spectra are presented for ethyl, n-propyl, and n-butylbenzene. With the aid of a local mode Hamiltonian that includes the effects of stretch-scissor Fermi resonance, the spectra can be accurately modeled for specific conformers. These molecules allow for further development of a first principles method for calculating alkyl stretch spectra. Across all chain lengths, certain dihedral patterns impart particular spectral motifs at the quadratic level. However, the anharmonic contributions are consistent from molecule to molecule and conformer to conformer. This transferability of anharmonicities allows for the Hamiltonian to be constructed from only a harmonic frequency calculation, reducing the cost of the model. Finally, the phenyl ring alters the frequencies of the CH2 stretches by about 15 cm-1 compared to their n-alkane counterparts in trans configurations. Conformational changes in the chain can lead to shifts in frequency of up to 30 cm-1.},
doi = {10.1063/1.4953181},
journal = {Journal of Chemical Physics},
number = 22,
volume = 144,
place = {United States},
year = {Tue Jun 14 00:00:00 EDT 2016},
month = {Tue Jun 14 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Efficient anharmonic vibrational spectroscopy for large molecules using local-mode coordinates
journal, September 2014
- Cheng, Xiaolu; Steele, Ryan P.
- The Journal of Chemical Physics, Vol. 141, Issue 10
The Infrared and Ultraviolet Spectra of Individual Conformational Isomers of Biomolecules: Tryptamine
journal, September 2000
- Carney, Joel R.; Zwier, Timothy S.
- The Journal of Physical Chemistry A, Vol. 104, Issue 38
Beyond Local Group Modes in Vibrational Sum Frequency Generation
journal, March 2015
- Chase, Hilary M.; Psciuk, Brian T.; Strick, Benjamin L.
- The Journal of Physical Chemistry A, Vol. 119, Issue 14
Stretching and folding of 2-nanometer hydrocarbon rods
journal, January 2014
- Lüttschwager, Nils O. B.; Suhm, Martin A.
- Soft Matter, Vol. 10, Issue 27
Carbon-hydrogen stretching modes and the structure of n-alkyl chains. 2. Long, all-trans chains
journal, February 1984
- MacPhail, R. A.; Strauss, H. L.; Snyder, R. G.
- The Journal of Physical Chemistry, Vol. 88, Issue 3
Mode‐selective photoisomerization in 5‐hydroxytropolone. I. Experiment
journal, April 1995
- Ensminger, Frederick A.; Plassard, Jason; Zwier, Timothy S.
- The Journal of Chemical Physics, Vol. 102, Issue 13
Fermi Resonance Effects in the Vibrational Spectroscopy of Methyl and Methoxy Groups
journal, November 2014
- Sibert, Edwin L.; Tabor, Daniel P.; Kidwell, Nathanael M.
- The Journal of Physical Chemistry A, Vol. 118, Issue 47
Infrared and Ultraviolet Spectral Signatures and Conformational Preferences of Jet-Cooled Serotonin
journal, April 2007
- LeGreve, Tracy A.; Baquero, Esteban E.; Zwier, Timothy S.
- Journal of the American Chemical Society, Vol. 129, Issue 13
Infrared spectroscopy of CH stretching vibrations of jet-cooled alkylbenzene cations by using the “messenger” technique
journal, April 2000
- Fujii, Asuka; Fujimaki, Eiji; Ebata, Takayuki
- The Journal of Chemical Physics, Vol. 112, Issue 14
A Local-Mode Model for Understanding the Dependence of the Extended Amide III Vibrations on Protein Secondary Structure
journal, August 2010
- Weymuth, Thomas; Jacob, Christoph R.; Reiher, Markus
- The Journal of Physical Chemistry B, Vol. 114, Issue 32
Determination of Noncovalent Docking by Infrared Spectroscopy of Cold Gas-Phase Complexes
journal, January 2012
- Garand, E.; Kamrath, M. Z.; Jordan, P. A.
- Science, Vol. 335, Issue 6069
Optimizing Vibrational Coordinates To Modulate Intermode Coupling
journal, March 2016
- Zimmerman, Paul M.; Smereka, Peter
- Journal of Chemical Theory and Computation, Vol. 12, Issue 4
Local mode theory for C 3 v molecules: CH 3 D, CHD 3 , SiH 3 D, and SiHD 3
journal, November 1983
- Halonen, L.; Child, M. S.
- The Journal of Chemical Physics, Vol. 79, Issue 9
Optimized coordinates for anharmonic vibrational structure theories
journal, November 2012
- Yagi, Kiyoshi; Keçeli, Murat; Hirata, So
- The Journal of Chemical Physics, Vol. 137, Issue 20
Red-, Blue-, or No-Shift in Hydrogen Bonds: A Unified Explanation
journal, April 2007
- Joseph, Jorly; Jemmis, Eluvathingal D.
- Journal of the American Chemical Society, Vol. 129, Issue 15
A First-Principles Model of Fermi Resonance in the Alkyl CH Stretch Region: Application to Hydronaphthalenes, Indanes, and Cyclohexane
journal, April 2014
- Sibert, Edwin L.; Kidwell, Nathanael M.; Zwier, Timothy S.
- The Journal of Physical Chemistry B, Vol. 118, Issue 28
Vibrational relaxation in jet‐cooled alkyl benzenes. II. Fluorescence spectra
journal, May 1980
- Hopkins, J. B.; Powers, D. E.; Mukamel, S.
- The Journal of Chemical Physics, Vol. 72, Issue 9
Vibrational relaxation in jet‐cooled alkyl benzenes. I.Absorption spectra
journal, May 1980
- Hopkins, J. B.; Powers, D. E.; Smalley, R. E.
- The Journal of Chemical Physics, Vol. 72, Issue 9
Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates
journal, August 2008
- Battin-Leclerc, F.
- Progress in Energy and Combustion Science, Vol. 34, Issue 4
A high-pressure rapid compression machine study of n-propylbenzene ignition
journal, January 2014
- Darcy, D.; Nakamura, H.; Tobin, C. J.
- Combustion and Flame, Vol. 161, Issue 1
Exploring the relationship between vibrational mode locality and coupling using constrained optimization
journal, March 2016
- Molina, Andrew; Smereka, Peter; Zimmerman, Paul M.
- The Journal of Chemical Physics, Vol. 144, Issue 12
An experimental and modeling study of shock tube and rapid compression machine ignition of n-butylbenzene/air mixtures
journal, January 2014
- Nakamura, Hisashi; Darcy, Daniel; Mehl, Marco
- Combustion and Flame, Vol. 161, Issue 1
Conformationally induced transition moment rotations in the S1←S0 electronic spectra of n-propylbenzene and n-butylbenzene
journal, January 1997
- A. Dickinson, John; W. Joireman, Paul; T. Kroemer, Romano
- Journal of the Chemical Society, Faraday Transactions, Vol. 93, Issue 8
Dressed local mode Hamiltonians for CH stretch vibrations
journal, April 2013
- Sibert, Edwin L.
- Molecular Physics, Vol. 111, Issue 14-15
Efficient Calculation of Anharmonic Vibrational Spectra of Large Molecules with Localized Modes
journal, July 2014
- Panek, Paweł T.; Jacob, Christoph R.
- ChemPhysChem, Vol. 15, Issue 15
Localizing normal modes in large molecules
journal, February 2009
- Jacob, Christoph R.; Reiher, Markus
- The Journal of Chemical Physics, Vol. 130, Issue 8
Infrared Photodissociation Spectroscopy of n -Propylbenzene−Ar Cluster Cations: Charge Delocalization between the Aromatic Ring and the Alkyl Chain
journal, May 2001
- Fujimaki, Eiji; Fujii, Asuka; Ebata, Takayuki
- The Journal of Physical Chemistry A, Vol. 105, Issue 20
Coupled-monomers in molecular assemblies: Theory and application to the water tetramer, pentamer, and ring hexamer
journal, April 2012
- Wang, Yimin; Bowman, Joel M.
- The Journal of Chemical Physics, Vol. 136, Issue 14
A high pressure shock tube study of n-propylbenzene oxidation and its comparison with n-butylbenzene
journal, July 2012
- Darcy, Daniel; Tobin, Colin J.; Yasunaga, Kenji
- Combustion and Flame, Vol. 159, Issue 7
Carbon-hydrogen stretching modes and the structure of n-alkyl chains. 1. Long, disordered chains
journal, December 1982
- Snyder, R. G.; Strauss, H. L.; Elliger, C. A.
- The Journal of Physical Chemistry, Vol. 86, Issue 26
Local mode vibrations of water
journal, June 1979
- Lawton, R. T.; Child, M. S.
- Molecular Physics, Vol. 37, Issue 6
Isolated C–H stretching vibrations of n ‐alkanes: Assignments and relation to structure
journal, December 1984
- Snyder, Robert G.; Aljibury, A. L.; Strauss, Herbert L.
- The Journal of Chemical Physics, Vol. 81, Issue 12
High resolution electronic spectroscopy of three n -alkylbenzenes: ethyl-, propyl-, and butylbenzene
journal, April 2002
- Borst, David R.; Joireman, Paul W.; Pratt, David W.
- The Journal of Chemical Physics, Vol. 116, Issue 16
Ground State Conformational Preferences and CH Stretch–Bend Coupling in a Model Alkoxy Chain: 1,2-Diphenoxyethane
journal, February 2013
- Buchanan, Evan G.; Sibert, Edwin L.; Zwier, Timothy S.
- The Journal of Physical Chemistry A, Vol. 117, Issue 13
Vibrational analysis of the n-paraffins—I
journal, January 1963
- Snyder, R. G.; Schachtschneider, J. H.
- Spectrochimica Acta, Vol. 19, Issue 1
Isomer-Specific Spectroscopy of Benzene–(H 2 O) n , n = 6,7: Benzene’s Role in Reshaping Water’s Three-Dimensional Networks
journal, May 2015
- Tabor, Daniel P.; Kusaka, Ryoji; Walsh, Patrick S.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 10
Vibrational second-order perturbation theory (VPT2) using local monomer normal modes
journal, October 2015
- Yu, Qi; Bowman, Joel M.
- Molecular Physics, Vol. 113, Issue 24
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
The Last Globally Stable Extended Alkane
journal, August 2012
- Lüttschwager, Nils O. B.; Wassermann, Tobias N.; Mata, Ricardo A.
- Angewandte Chemie International Edition, Vol. 52, Issue 1
Microwave studies of three alkylbenzenes: Ethyl, n -propyl, and n -butylbenzene
journal, July 2000
- Maté, Belén; Suenram, Richard D.; Lugez, Catherine
- The Journal of Chemical Physics, Vol. 113, Issue 1
Towards a first-principles model of Fermi resonance in the alkyl CH stretch region: Application to 1,2-diphenylethane and 2,2,2-paracyclophane
journal, February 2013
- Buchanan, Evan G.; Dean, Jacob C.; Zwier, Timothy S.
- The Journal of Chemical Physics, Vol. 138, Issue 6
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
journal, January 2008
- Chai, Jeng-Da; Head-Gordon, Martin
- Physical Chemistry Chemical Physics, Vol. 10, Issue 44
Works referencing / citing this record:
Anharmonic interstellar PAH molecules: CANDIAN AND MACKIE
journal, September 2016
- Candian, Alessandra; Mackie, Cameron J.
- International Journal of Quantum Chemistry, Vol. 117, Issue 2
Halocarbons as hydrogen bond acceptors: a spectroscopic study of haloethylbenzenes (PhCH 2 CH 2 X, X = F, Cl, Br) and their hydrate clusters
journal, January 2018
- Robertson, Patrick A.; Villani, Luigi; Dissanayake, Uresha L. M.
- Physical Chemistry Chemical Physics, Vol. 20, Issue 12
Fermi resonance in solvated H 3 O + : a counter-intuitive trend confirmed via a joint experimental and theoretical investigation
journal, January 2018
- Huang, Qian-Rui; Nishigori, Tomoki; Katada, Marusu
- Physical Chemistry Chemical Physics, Vol. 20, Issue 20
Conformational explosion: Understanding the complexity of short chain para -dialkylbenzene potential energy surfaces
journal, May 2018
- Mishra, Piyush; Hewett, Daniel M.; Zwier, Timothy S.
- The Journal of Chemical Physics, Vol. 148, Issue 18
Modeling vibrational anharmonicity in infrared spectra of high frequency vibrations of polyatomic molecules
journal, March 2019
- Sibert, Edwin L.
- The Journal of Chemical Physics, Vol. 150, Issue 9