Infrared and Raman Spectroscopy from Ab Initio Molecular Dynamics and Static Normal Mode Analysis: The C-H Region of DMSO as a Case Study

Sean A. Fischer, Tyler W. Ueltschi, Patrick Z. El-Khoury, Amanda L. Mifflin, Wayne P. Hess, Hong Fei Wang, Chris Cramer, Niranjan Govind

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41 Scopus citations


Carbon-hydrogen (C-H) vibration modes serve as key probes in the chemical identification of hydrocarbons and in vibrational sum-frequency generation spectroscopy of hydrocarbons at the liquid/gas interface. Their assignments pose a challenge from a theoretical viewpoint. In this work, we present a detailed study of the C-H stretching region of dimethyl sulfoxide using a new ab initio molecular dynamics (AIMD) module that we have implemented in NWChem. Through a combination of AIMD simulations and static normal mode analysis, we interpret experimental infrared and Raman spectra and explore the role of anharmonic effects in this system. Comprehensive anharmonic normal mode analysis of the C-H stretching region casts doubt upon previous experimental assignments of the shoulder on the symmetric C-H stretching peak. In addition, our AIMD simulations also show significant broadening of the in-phase symmetric C-H stretching resonance, which suggests that the experimentally observed shoulder is due to thermal broadening of the symmetric stretching resonance. (Graph Presented).

Original languageEnglish (US)
Pages (from-to)1429-1436
Number of pages8
JournalJournal of Physical Chemistry B
Issue number8
StatePublished - Mar 3 2016

Bibliographical note

Funding Information:
This material is based on work supported by the U.S. Department of Energy (DOE), Office of Science, Office of Advanced Scientific Computing Research, Scientific Discovery through Advanced Computing (SciDAC) program under Award Numbers DE-SC0008666 (C.J.C.) and KC030102062653 (S.A.F, N.G.). P.Z.E. acknowledges support from the Laboratory Directed Research and Development Program through a Linus Pauling Fellowship at Pacific Northwest National Laboratory (PNNL) and an allocation of computing time from the National Science Foundation (TGCHE130003). W.P.H. acknowledges support from the U.S. DOE, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences under Award Number KC030102016248. T.W.U. and A.L.M. were supported in part by the U.S. DOE, Office of Science, Office of Workforce Development for Teachers and Scientists (WDTS) under the Visiting Faculty Program (VFP). This work also benefitted from resources provided by PNNL Institutional Computing. This research was performed using EMSL, a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle Memorial Institute for the United States Department of Energy under DOE contract number DE-AC05-76RL1830.

Publisher Copyright:
© 2015 American Chemical Society.


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