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

Journal Article · · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
 [1];  [2];  [3];  [2];  [3];  [1];  [4];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
  2. Univ. of Puget Sound, Tacoma, WA (United States). Dept. of Chemistry
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division
  4. Univ. of Minnesota, Minneapolis, MN (United States). Supercomputing Inst. and Chemical Theory Center, Dept. of Chemistry
+ Show Author Affiliations

Carbon-hydrogen (C-H) vibration modes serve as key probes in the chemical identification of hydrocarbons and in vibrational sum-frequency generation (SFG) spectroscopy of hydrocarbons at the liquid/gas interface. Their assignments pose a challenge from a theoretical viewpoint. Here in this work, we present a detailed study of the C-H stretching region of dimethyl sulfoxide (DMSO) using a new Gaussian basis set- based ab initio molecular dynamics (AIMD) module that we have implemented in the NWChem computational chemistry program. By combining AIMD simulations and static normal mode analysis, we interpret experimental infrared and Raman spectra and explore the role of anharmonic effects in this system. Our anharmonic normal mode analysis of the in-phase and out-of-phase symmetric C-H stretching modes challenges the previous experimental assignment of the shoulder in the symmetric C-H stretching peak as an overtone or Fermi resonance. 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.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR); National Science Foundation (NSF); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC05-76RL01830; SC0008666
OSTI ID:
1254566
Report Number(s):
PNNL-SA-109387; 48664; KC0301050
Journal Information:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 120, Issue 8; ISSN 1520-6106
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 38 works
Citation information provided by
Web of Science

References (61)

Chemical imaging of tissue in vivo with video-rate coherent anti-Stokes Raman scattering microscopy journal November 2005
Label-Free Biomedical Imaging with High Sensitivity by Stimulated Raman Scattering Microscopy journal December 2008
Biomolecular Imaging with Coherent Nonlinear Vibrational Microscopy journal April 2013
C−H Stretching Vibrations of Methyl, Methylene and Methine Groups at the Vapor/Alcohol ( n = 1−8) Interfaces journal July 2005
Communication: Spectroscopic phase and lineshapes in high-resolution broadband sum frequency vibrational spectroscopy: Resolving interfacial inhomogeneities of “identical” molecular groups journal December 2011
Unified treatment and measurement of the spectral resolution and temporal effects in frequency-resolved sum-frequency generation vibrational spectroscopy (SFG-VS) journal January 2013
Systematic ab initio gradient calculation of molecular geometries, force constants, and dipole moment derivatives journal May 1979
Uncertainties in Scaling Factors for ab Initio Vibrational Frequencies journal September 2005
Computational Thermochemistry: Scale Factor Databases and Scale Factors for Vibrational Frequencies Obtained from Electronic Model Chemistries journal August 2010
The self-consistent-field approach to polyatomic vibrations journal June 1986
Vibrational Spectroscopy of the G· · ·C Base Pair:  Experiment, Harmonic and Anharmonic Calculations, and the Nature of the Anharmonic Couplings journal August 2005
Anharmonic Vibrational Spectroscopy of Glycine:  Testing of ab Initio and Empirical Potentials journal November 2000
Raman spectra of long chain hydrocarbons: anharmonic calculations, experiment and implications for imaging of biomembranes journal January 2011
First-principles calculations of anharmonic vibrational spectroscopy of large molecules book January 2005
Vibrational wave functions and spectroscopy of (H 2 O) n , n =2,3,4,5: Vibrational self‐consistent field with correlation corrections journal December 1996
Vibrational Spectra of α-Glucose, β-Glucose, and Sucrose: Anharmonic Calculations and Experiment journal June 2011
Vibrational structure theory: new vibrational wave function methods for calculation of anharmonic vibrational energies and vibrational contributions to molecular properties journal January 2007
Anharmonic vibrational properties by a fully automated second-order perturbative approach journal January 2005
On the Calculation of Vibrational Frequencies for Molecules in Solution Beyond the Harmonic Approximation journal April 2010
Unexpected Hydrogen Bond Dynamics in Imidazolium-Based Ionic Liquids journal November 2009
Effect of Dispersion on the Structure and Dynamics of the Ionic Liquid 1-Ethyl-3-methylimidazolium Thiocyanate journal March 2012
The bulk and the gas phase of 1-ethyl-3-methylimidazolium ethylsulfate: dispersion interaction makes the difference journal January 2012
On the ideality of binary mixtures of ionic liquids journal January 2012
Proton transfer and polarity changes in ionic liquid–water mixtures: a perspective on hydrogen bonds from ab initio molecular dynamics at the example of 1-ethyl-3-methylimidazolium acetate–water mixtures—Part 1 journal January 2012
Real-World Predictions from Ab Initio Molecular Dynamics Simulations book January 2011
Isobaric−Isothermal Molecular Dynamics Simulations Utilizing Density Functional Theory: An Assessment of the Structure and Density of Water at Near-Ambient Conditions journal September 2009
Proton Transfer 200 Years after von Grotthuss: Insights from Ab Initio Simulations journal September 2006
Unified Approach for Molecular Dynamics and Density-Functional Theory journal November 1985
Computing vibrational spectra from ab initio molecular dynamics journal January 2013
Simulations of vibrational spectra from classical trajectories: Calibration with ab initio force fields journal August 2007
Correction of Vibrational Broadening in Molecular Dynamics Clusters with the Normal Mode Optimization Method journal December 2011
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations journal September 2010
Quantitative Sum-Frequency Generation Vibrational Spectroscopy of Molecular Surfaces and Interfaces: Lineshape, Polarization, and Orientation journal April 2015
Accurate Line Shapes from Sub-1 cm –1 Resolution Sum Frequency Generation Vibrational Spectroscopy of α-Pinene at Room Temperature journal February 2015
Quantum corrections to classical time-correlation functions: Hydrogen bonding and anharmonic floppy modes journal September 2004
Simulating One-Photon Absorption and Resonance Raman Scattering Spectra Using Analytical Excited State Energy Gradients within Time-Dependent Density Functional Theory journal November 2013
A computer simulation method for the calculation of equilibrium constants for the formation of physical clusters of molecules: Application to small water clusters journal January 1982
Canonical sampling through velocity rescaling journal January 2007
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis journal August 1980
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions journal January 1980
Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18 journal May 1980
Raman scattering and DFT calculations used for analyzing the structural features of DMSO in water and methanol journal January 2013
Calculation of optical rotation with time-periodic magnetic-field-dependent basis functions in approximate time-dependent density-functional theory journal September 2005
Finite lifetime effects on the polarizability within time-dependent density-functional theory journal June 2005
Calculation of Verdet constants with time-dependent density functional theory: Implementation and results for small molecules journal February 2005
Accurate dipole polarizabilities for water clusters n=2–12 at the coupled-cluster level of theory and benchmarking of various density functionals journal December 2009
Time-Dependent Density Functional Methods for Raman Spectra in Open-Shell Systems journal January 2014
On the use of windows for harmonic analysis with the discrete Fourier transform journal January 1978
New Scale Factors for Harmonic Vibrational Frequencies Using the B3LYP Density Functional Method with the Triple-ζ Basis Set 6-311+G(d,p) journal March 2005
Infrared and Raman spectra and normal co-ordinate analysis of dimethyl sulfoxide and dimethyl sulfoxide-d6 journal January 1961
Spectres de vibration du diméthylsulfoxyde et dn diméthylsulfoxyde-d6 journal May 1970
Improving anharmonic infrared spectra using semiclassically prepared molecular dynamics simulations journal January 2012
Nuclear Quantum Effects in Solids Using a Colored-Noise Thermostat journal July 2009
Colored-Noise Thermostats à la Carte journal March 2010
New C−H Stretching Vibrational Spectral Features in the Raman Spectra of Gaseous and Liquid Ethanol † journal June 2007
Complete Raman Spectral Assignment of Methanol in the C–H Stretching Region journal May 2013
Comparison study of the prediction of Raman intensities using electronic structure methods journal November 1999
Basis Set Dependence of Vibrational Raman and Raman Optical Activity Intensities journal August 2011
Raman spectrum of dimethyl sulfoxide (DMSO) and the influence of solvents journal July 1966
Molecular Structure and Adsorption of Dimethyl Sulfoxide at the Surface of Aqueous Solutions journal January 1999

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Machine learning molecular dynamics for the simulation of infrared spectra journal January 2017
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Quantum chemical investigation of the detection properties of alternariol and alternariol monomethyl ether journal March 2019
Newly proposed proton-abstraction roundabout with backside attack mechanism for the S N 2 reaction at the nitrogen center in F − + NH 2 Cl journal January 2018
Atmospheric particulate matter characterization by Fourier transform infrared spectroscopy: a review of statistical calibration strategies for carbonaceous aerosol quantification in US measurement networks journal January 2019
Atmospheric particulate matter characterization by Fourier Transform Infrared spectroscopy: a review of statistical calibration strategies for carbonaceous aerosol quantification in US measurement networks posted_content July 2018
Theoretical investigation of cyromazine tautomerism using density functional theory and Møller–Plesset perturbation theory methods text January 2018
Theoretical investigation of cyromazine tautomerism using density functional theory and Møller–Plesset perturbation theory methods text January 2018
Efficiently Calculating Anharmonic Frequencies of Molecular Vibration by Molecular Dynamics Trajectory Analysis journal May 2019
Probe of Alcohol Structures in the Gas and Liquid States Using C–H Stretching Raman Spectroscopy journal June 2018
Machine Learning Molecular Dynamics for the Simulation of Infrared Spectra text January 2017

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