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Title: 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:
 [1]; ORCiD logo [2];  [2]; ORCiD logo [2];  [2];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry. Theoretical Chemistry Inst.
  2. 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) (SC-22); 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. 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, Edwin L. Tue . "Anharmonic modeling of the conformation-specific IR spectra of ethyl, n-propyl, and n-butylbenzene". United States. doi: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 = {2016},
month = {6}
}

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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
  • DOI: 10.1063/1.4894507

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
  • DOI: 10.1021/jp001433r

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
  • DOI: 10.1021/acs.jpca.5b02208

Stretching and folding of 2-nanometer hydrocarbon rods
journal, January 2014

  • Lüttschwager, Nils O. B.; Suhm, Martin A.
  • Soft Matter, Vol. 10, Issue 27
  • DOI: 10.1039/C4SM00508B

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
  • DOI: 10.1021/j150647a002

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
  • DOI: 10.1063/1.469250

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
  • DOI: 10.1021/jp510142g

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
  • DOI: 10.1021/ja068881i

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
  • DOI: 10.1063/1.481272

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
  • DOI: 10.1021/jp104542w

Determination of Noncovalent Docking by Infrared Spectroscopy of Cold Gas-Phase Complexes
journal, January 2012


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
  • DOI: 10.1021/acs.jctc.5b01168

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
  • DOI: 10.1063/1.446317

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
  • DOI: 10.1063/1.4767776

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
  • DOI: 10.1021/ja067545z

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
  • DOI: 10.1021/jp5014048

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
  • DOI: 10.1063/1.439794

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
  • DOI: 10.1063/1.439793

A high-pressure rapid compression machine study of n-propylbenzene ignition
journal, January 2014


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
  • DOI: 10.1063/1.4944743

An experimental and modeling study of shock tube and rapid compression machine ignition of n-butylbenzene/air mixtures
journal, January 2014


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
  • DOI: 10.1039/a608012j

Dressed local mode Hamiltonians for CH stretch vibrations
journal, April 2013


Efficient Calculation of Anharmonic Vibrational Spectra of Large Molecules with Localized Modes
journal, July 2014


Localizing normal modes in large molecules
journal, February 2009

  • Jacob, Christoph R.; Reiher, Markus
  • The Journal of Chemical Physics, Vol. 130, Issue 8
  • DOI: 10.1063/1.3077690

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
  • DOI: 10.1021/jp004557c

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
  • DOI: 10.1063/1.3700165

A high pressure shock tube study of n-propylbenzene oxidation and its comparison with n-butylbenzene
journal, July 2012


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
  • DOI: 10.1021/j100223a018

Local mode vibrations of water
journal, June 1979


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
  • DOI: 10.1063/1.447677

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
  • DOI: 10.1063/1.1462578

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
  • DOI: 10.1021/jp400691a

Vibrational analysis of the n-paraffins—I
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
journal, May 2015

  • Tabor, Daniel P.; Kusaka, Ryoji; Walsh, Patrick S.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 10
  • DOI: 10.1021/acs.jpclett.5b00786

Vibrational second-order perturbation theory (VPT2) using local monomer normal modes
journal, October 2015


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
  • DOI: 10.1063/1.3382344

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
  • DOI: 10.1002/anie.201202894

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
  • DOI: 10.1063/1.481818

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
  • DOI: 10.1063/1.4790163

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
  • DOI: 10.1039/b810189b