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

Tabor, Daniel P.; Hewett, Daniel M.; Bocklitz, Sebastian; Korn, Joseph A.; Tomaine, Anthony J.; Ghosh, Arun K.; Zwier, Timothy S.; Sibert, Edwin L.

doi:10.1063/1.4953181

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

Journal Article · Tue Jun 14 00:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4953181· OSTI ID:1471526

Tabor, Daniel P. ^[1];

^[2]; Bocklitz, Sebastian ^[2];

^[2]; Tomaine, Anthony J. ^[2]; Ghosh, Arun K. ^[2];

^[2];

^[1]

Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry. Theoretical Chemistry Inst.
Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry

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.

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Research Organization:: Purdue Univ., West Lafayette, IN (United States); Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); German Research Foundation (DFG)

Grant/Contract Number:: FG02-96ER14656; CHE-1213449; SU 121/6-1

OSTI ID:: 1471526

Alternate ID(s):: OSTI ID: 1257004

Journal Information:: Journal of Chemical Physics, Vol. 144, Issue 22; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 28 works

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References (42)

Efficient anharmonic vibrational spectroscopy for large molecules using local-mode coordinates Cheng, Xiaolu; Steele, Ryan P. The Journal of Chemical Physics, Vol. 141, Issue 10 https://doi.org/10.1063/1.4894507	journal	September 2014
The Infrared and Ultraviolet Spectra of Individual Conformational Isomers of Biomolecules: Tryptamine Carney, Joel R.; Zwier, Timothy S. The Journal of Physical Chemistry A, Vol. 104, Issue 38 https://doi.org/10.1021/jp001433r	journal	September 2000
Beyond Local Group Modes in Vibrational Sum Frequency Generation Chase, Hilary M.; Psciuk, Brian T.; Strick, Benjamin L. The Journal of Physical Chemistry A, Vol. 119, Issue 14 https://doi.org/10.1021/acs.jpca.5b02208	journal	March 2015
Stretching and folding of 2-nanometer hydrocarbon rods Lüttschwager, Nils O. B.; Suhm, Martin A. Soft Matter, Vol. 10, Issue 27 https://doi.org/10.1039/C4SM00508B	journal	January 2014
Carbon-hydrogen stretching modes and the structure of n-alkyl chains. 2. Long, all-trans chains MacPhail, R. A.; Strauss, H. L.; Snyder, R. G. The Journal of Physical Chemistry, Vol. 88, Issue 3 https://doi.org/10.1021/j150647a002	journal	February 1984
Mode‐selective photoisomerization in 5‐hydroxytropolone. I. Experiment Ensminger, Frederick A.; Plassard, Jason; Zwier, Timothy S. The Journal of Chemical Physics, Vol. 102, Issue 13 https://doi.org/10.1063/1.469250	journal	April 1995
Fermi Resonance Effects in the Vibrational Spectroscopy of Methyl and Methoxy Groups Sibert, Edwin L.; Tabor, Daniel P.; Kidwell, Nathanael M. The Journal of Physical Chemistry A, Vol. 118, Issue 47 https://doi.org/10.1021/jp510142g	journal	November 2014
Infrared and Ultraviolet Spectral Signatures and Conformational Preferences of Jet-Cooled Serotonin LeGreve, Tracy A.; Baquero, Esteban E.; Zwier, Timothy S. Journal of the American Chemical Society, Vol. 129, Issue 13 https://doi.org/10.1021/ja068881i	journal	April 2007
Infrared spectroscopy of CH stretching vibrations of jet-cooled alkylbenzene cations by using the “messenger” technique Fujii, Asuka; Fujimaki, Eiji; Ebata, Takayuki The Journal of Chemical Physics, Vol. 112, Issue 14 https://doi.org/10.1063/1.481272	journal	April 2000
A Local-Mode Model for Understanding the Dependence of the Extended Amide III Vibrations on Protein Secondary Structure Weymuth, Thomas; Jacob, Christoph R.; Reiher, Markus The Journal of Physical Chemistry B, Vol. 114, Issue 32 https://doi.org/10.1021/jp104542w	journal	August 2010
Determination of Noncovalent Docking by Infrared Spectroscopy of Cold Gas-Phase Complexes Garand, E.; Kamrath, M. Z.; Jordan, P. A. Science, Vol. 335, Issue 6069 https://doi.org/10.1126/science.1214948	journal	January 2012
Optimizing Vibrational Coordinates To Modulate Intermode Coupling Zimmerman, Paul M.; Smereka, Peter Journal of Chemical Theory and Computation, Vol. 12, Issue 4 https://doi.org/10.1021/acs.jctc.5b01168	journal	March 2016
Local mode theory for C _{3 v} molecules: CH ₃ D, CHD ₃ , SiH ₃ D, and SiHD ₃ Halonen, L.; Child, M. S. The Journal of Chemical Physics, Vol. 79, Issue 9 https://doi.org/10.1063/1.446317	journal	November 1983
Optimized coordinates for anharmonic vibrational structure theories Yagi, Kiyoshi; Keçeli, Murat; Hirata, So The Journal of Chemical Physics, Vol. 137, Issue 20 https://doi.org/10.1063/1.4767776	journal	November 2012
Red-, Blue-, or No-Shift in Hydrogen Bonds: A Unified Explanation Joseph, Jorly; Jemmis, Eluvathingal D. Journal of the American Chemical Society, Vol. 129, Issue 15 https://doi.org/10.1021/ja067545z	journal	April 2007
A First-Principles Model of Fermi Resonance in the Alkyl CH Stretch Region: Application to Hydronaphthalenes, Indanes, and Cyclohexane Sibert, Edwin L.; Kidwell, Nathanael M.; Zwier, Timothy S. The Journal of Physical Chemistry B, Vol. 118, Issue 28 https://doi.org/10.1021/jp5014048	journal	April 2014
Vibrational relaxation in jet‐cooled alkyl benzenes. II. Fluorescence spectra Hopkins, J. B.; Powers, D. E.; Mukamel, S. The Journal of Chemical Physics, Vol. 72, Issue 9 https://doi.org/10.1063/1.439794	journal	May 1980
Vibrational relaxation in jet‐cooled alkyl benzenes. I.Absorption spectra Hopkins, J. B.; Powers, D. E.; Smalley, R. E. The Journal of Chemical Physics, Vol. 72, Issue 9 https://doi.org/10.1063/1.439793	journal	May 1980
Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates Battin-Leclerc, F. Progress in Energy and Combustion Science, Vol. 34, Issue 4 https://doi.org/10.1016/j.pecs.2007.10.002	journal	August 2008
A high-pressure rapid compression machine study of n-propylbenzene ignition Darcy, D.; Nakamura, H.; Tobin, C. J. Combustion and Flame, Vol. 161, Issue 1 https://doi.org/10.1016/j.combustflame.2013.08.001	journal	January 2014
Exploring the relationship between vibrational mode locality and coupling using constrained optimization Molina, Andrew; Smereka, Peter; Zimmerman, Paul M. The Journal of Chemical Physics, Vol. 144, Issue 12 https://doi.org/10.1063/1.4944743	journal	March 2016
An experimental and modeling study of shock tube and rapid compression machine ignition of n-butylbenzene/air mixtures Nakamura, Hisashi; Darcy, Daniel; Mehl, Marco Combustion and Flame, Vol. 161, Issue 1 https://doi.org/10.1016/j.combustflame.2013.08.002	journal	January 2014
Conformationally induced transition moment rotations in the S1←S0 electronic spectra of n-propylbenzene and n-butylbenzene A. Dickinson, John; W. Joireman, Paul; T. Kroemer, Romano Journal of the Chemical Society, Faraday Transactions, Vol. 93, Issue 8 https://doi.org/10.1039/a608012j	journal	January 1997
Dressed local mode Hamiltonians for CH stretch vibrations Sibert, Edwin L. Molecular Physics, Vol. 111, Issue 14-15 https://doi.org/10.1080/00268976.2013.783939	journal	April 2013
Efficient Calculation of Anharmonic Vibrational Spectra of Large Molecules with Localized Modes Panek, Paweł T.; Jacob, Christoph R. ChemPhysChem, Vol. 15, Issue 15 https://doi.org/10.1002/cphc.201402251	journal	July 2014
Localizing normal modes in large molecules Jacob, Christoph R.; Reiher, Markus The Journal of Chemical Physics, Vol. 130, Issue 8 https://doi.org/10.1063/1.3077690	journal	February 2009
Infrared Photodissociation Spectroscopy of n -Propylbenzene−Ar Cluster Cations: Charge Delocalization between the Aromatic Ring and the Alkyl Chain Fujimaki, Eiji; Fujii, Asuka; Ebata, Takayuki The Journal of Physical Chemistry A, Vol. 105, Issue 20 https://doi.org/10.1021/jp004557c	journal	May 2001
Coupled-monomers in molecular assemblies: Theory and application to the water tetramer, pentamer, and ring hexamer Wang, Yimin; Bowman, Joel M. The Journal of Chemical Physics, Vol. 136, Issue 14 https://doi.org/10.1063/1.3700165	journal	April 2012
A high pressure shock tube study of n-propylbenzene oxidation and its comparison with n-butylbenzene Darcy, Daniel; Tobin, Colin J.; Yasunaga, Kenji Combustion and Flame, Vol. 159, Issue 7 https://doi.org/10.1016/j.combustflame.2012.02.009	journal	July 2012
Carbon-hydrogen stretching modes and the structure of n-alkyl chains. 1. Long, disordered chains Snyder, R. G.; Strauss, H. L.; Elliger, C. A. The Journal of Physical Chemistry, Vol. 86, Issue 26 https://doi.org/10.1021/j100223a018	journal	December 1982
Local mode vibrations of water Lawton, R. T.; Child, M. S. Molecular Physics, Vol. 37, Issue 6 https://doi.org/10.1080/00268977900101331	journal	June 1979
Isolated C–H stretching vibrations of n ‐alkanes: Assignments and relation to structure Snyder, Robert G.; Aljibury, A. L.; Strauss, Herbert L. The Journal of Chemical Physics, Vol. 81, Issue 12 https://doi.org/10.1063/1.447677	journal	December 1984
High resolution electronic spectroscopy of three n -alkylbenzenes: ethyl-, propyl-, and butylbenzene Borst, David R.; Joireman, Paul W.; Pratt, David W. The Journal of Chemical Physics, Vol. 116, Issue 16 https://doi.org/10.1063/1.1462578	journal	April 2002
Ground State Conformational Preferences and CH Stretch–Bend Coupling in a Model Alkoxy Chain: 1,2-Diphenoxyethane Buchanan, Evan G.; Sibert, Edwin L.; Zwier, Timothy S. The Journal of Physical Chemistry A, Vol. 117, Issue 13 https://doi.org/10.1021/jp400691a	journal	February 2013
Vibrational analysis of the n-paraffins—I Snyder, R. G.; Schachtschneider, J. H. Spectrochimica Acta, Vol. 19, Issue 1 https://doi.org/10.1016/0371-1951(63)80095-8	journal	January 1963
Isomer-Specific Spectroscopy of Benzene–(H ₂ O) _n , n = 6,7: Benzene’s Role in Reshaping Water’s Three-Dimensional Networks Tabor, Daniel P.; Kusaka, Ryoji; Walsh, Patrick S. The Journal of Physical Chemistry Letters, Vol. 6, Issue 10 https://doi.org/10.1021/acs.jpclett.5b00786	journal	May 2015
Vibrational second-order perturbation theory (VPT2) using local monomer normal modes Yu, Qi; Bowman, Joel M. Molecular Physics, Vol. 113, Issue 24 https://doi.org/10.1080/00268976.2015.1085109	journal	October 2015
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
The Last Globally Stable Extended Alkane Lüttschwager, Nils O. B.; Wassermann, Tobias N.; Mata, Ricardo A. Angewandte Chemie International Edition, Vol. 52, Issue 1 https://doi.org/10.1002/anie.201202894	journal	August 2012
Microwave studies of three alkylbenzenes: Ethyl, n -propyl, and n -butylbenzene Maté, Belén; Suenram, Richard D.; Lugez, Catherine The Journal of Chemical Physics, Vol. 113, Issue 1 https://doi.org/10.1063/1.481818	journal	July 2000
Towards a first-principles model of Fermi resonance in the alkyl CH stretch region: Application to 1,2-diphenylethane and 2,2,2-paracyclophane Buchanan, Evan G.; Dean, Jacob C.; Zwier, Timothy S. The Journal of Chemical Physics, Vol. 138, Issue 6 https://doi.org/10.1063/1.4790163	journal	February 2013
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections Chai, Jeng-Da; Head-Gordon, Martin Physical Chemistry Chemical Physics, Vol. 10, Issue 44 https://doi.org/10.1039/b810189b	journal	January 2008

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

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