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

Research output: Contribution to journalArticle

25 Scopus citations

Abstract

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
Volume120
Issue number8
DOIs
StatePublished - Mar 3 2016

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