Orientational time correlation functions for vibrational sum-frequency generation. 2. Propionitrile.

Molecular dynamics (MD) simulations of propionitrile have been performed to assess the influence of reorientation on vibrational sum-frequency-generation (VSFG) spectra at the liquid/vapor (LV) and liquid/silica (LS) interfaces. Orientational time-correlation functions (TCFs) are derived for the VSFG spectroscopy of the symmetric and asymmetric stretches of functional groups such as methylene groups and rotationally hindered methyl groups. The MD simulations are used to compute VSFG orientational TCFs for the methyl, methylene, and cyanide groups of propionitrile at the LV and LS interfaces. Although propionitrile exhibits relatively fast reorientation in the bulk liquid, we find that for symmetric stretching modes at these interfaces, reorientation only plays a significant role in VSFG spectra under SPS polarization conditions. For asymmetric stretches, reorientation affects the VSFG spectra significantly under all polarization conditions. Azimuthal dynamics tend to dominate the orientational TCFs.

[1]  W. Thompson,et al.  Grand canonical Monte Carlo simulations of acetonitrile filling of silica pores of varying hydrophilicity/hydrophobicity. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[2]  V. Ostroverkhov,et al.  Sum-frequency vibrational spectroscopy on water interfaces: polar orientation of water molecules at interfaces. , 2006, Chemical reviews.

[3]  D. Dlott,et al.  Vibrational energy in molecules probed with high time and space resolution , 2007 .

[4]  M. Himmelhaus,et al.  Vibrational spectroscopy of interfaces by infrared-visible sum frequency generation , 2001 .

[5]  K. Eisenthal,et al.  Liquid Interfaces Probed by Second-Harmonic and Sum-Frequency Spectroscopy. , 1996, Chemical reviews.

[6]  P. Pieniazek,et al.  Interpretation of the water surface vibrational sum-frequency spectrum. , 2011, The Journal of chemical physics.

[7]  J. Fourkas,et al.  Effects of Reorientation in Vibrational Sum-Frequency Spectroscopy† , 2007 .

[8]  J. Sung,et al.  Motional Effect on the Sum-Frequency Vibrational Spectra from Methanol Surface , 2007 .

[9]  R. Righini,et al.  Ultrafast Optical Kerr Effect in Liquids and Solids , 1993, Science.

[10]  C. Morales,et al.  Simulations of infrared spectra of nanoconfined liquids: acetonitrile confined in nanoscale, hydrophilic silica pores. , 2009, The journal of physical chemistry. A.

[11]  J. Skinner,et al.  Vibrational sum-frequency spectroscopy of the liquid/vapor interface for dilute HOD in D(2)O. , 2008, The Journal of chemical physics.

[12]  P. M. Rodger,et al.  DL_POLY: Application to molecular simulation , 2002 .

[13]  William L. Jorgensen,et al.  Gas‐phase and liquid‐state properties of esters, nitriles, and nitro compounds with the OPLS‐AA force field , 2001, J. Comput. Chem..

[14]  R. Farrer,et al.  DYNAMICS OF A WETTING LIQUID IN NANOPORES : AN OPTICAL KERR EFFECT STUDY OF THE DYNAMICS OF ACETONITRILE CONFINED IN SOL-GEL GLASSES , 1999 .

[15]  Y. Shen,et al.  Motional effect in surface sum-frequency vibrational spectroscopy. , 2001, Physical review letters.

[16]  G. Somorjai,et al.  Molecular Studies of Catalytic Reactions on Crystal Surfaces at High Pressures and High Temperatures by Infrared−Visible Sum Frequency Generation (SFG) Surface Vibrational Spectroscopy , 1999 .

[17]  J. Fourkas,et al.  Orientational time correlation functions for vibrational sum-frequency generation. 1. Acetonitrile. , 2013, The journal of physical chemistry. A.

[18]  W. Gan,et al.  Polarization and experimental configuration analyses of sum frequency generation vibrational spectra, structure, and orientational motion of the air/water interface. , 2005, The Journal of chemical physics.

[19]  W. Gan,et al.  Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS) , 2005 .

[20]  Hong-Fei Wang,et al.  Quantitative measurement and interpretation of optical second harmonic generation from molecular interfaces. , 2006, Physical chemistry chemical physics : PCCP.

[21]  Anan Liu,et al.  Microscopic molecular optics theory of surface second harmonic generation and sum-frequency generation spectroscopy based on the discrete dipole lattice model , 2008 .

[22]  N. T. Hunt,et al.  Ultrafast dynamics in complex fluids observed through the ultrafast optically-heterodyne-detected optical-Kerr-effect (OHD-OKE). , 2007, Physical chemistry chemical physics : PCCP.

[23]  Qin Zhong,et al.  Optical Kerr effect spectroscopy of simple liquids. , 2008, The journal of physical chemistry. B.

[24]  J. Fourkas,et al.  Structure of Liquid Propionitrile at Interfaces. 2. Experiment , 2012 .

[25]  M. Fayer,et al.  Theory of interfacial orientational relaxation spectroscopic observables. , 2010, The Journal of chemical physics.

[26]  R. Pecora,et al.  Time‐correlation functions for restricted rotational diffusion , 1980 .

[27]  R. Farrer,et al.  Orientational diffusion of n-alkyl cyanides , 2005 .

[28]  J. Skinner,et al.  Vibrational sum-frequency spectroscopy of the water liquid/vapor interface. , 2009, The journal of physical chemistry. B.

[29]  J. Weeks,et al.  Interfacial Organization of Acetonitrile: Simulation and Experiment , 2010 .

[30]  G. Richmond,et al.  Molecular bonding and interactions at aqueous surfaces as probed by vibrational sum frequency spectroscopy. , 2002, Chemical reviews.

[31]  J. Fourkas,et al.  Reorientation-induced spectral diffusion in vibrational sum-frequency-generation spectroscopy. , 2013, The journal of physical chemistry. B.

[32]  J. Weeks,et al.  Acetonitrile on Silica Surfaces and at Its Liquid−Vapor Interface: Structural Correlations and Collective Dynamics , 2010, 1009.3092.

[33]  U. Mohanty,et al.  Exponential intermolecular dynamics in optical Kerr effect spectroscopy of small-molecule liquids , 1999 .

[34]  Peter J. Rossky,et al.  A comparison of the structure and dynamics of liquid water at hydrophobic and hydrophilic surfaces—a molecular dynamics simulation study , 1994 .

[35]  Y. Wang,et al.  Treatment of Linear and Nonlinear Dielectric Property of Molecular Monolayer and Submonolayer with Microscopic Dipole Lattice Model: I. Second Harmonic Generation and Sum-Frequency Generation , 2007, 0708.1754.

[36]  Joseph A Morrone,et al.  Structure and Dynamics of Acetonitrile Confined in a Silica Nanopore , 2012 .

[37]  J. Fourkas,et al.  Reexamining the interpretation of vibrational sum-frequency generation spectra , 2011 .

[38]  Alexander V. Benderskii,et al.  Hydrogen bonding at the water surface revealed by isotopic dilution spectroscopy , 2011, Nature.

[39]  M. Berkowitz,et al.  Ewald summation for systems with slab geometry , 1999 .

[40]  J. Weeks,et al.  Structure of Liquid Propionitrile at Interfaces. 1. Molecular Dynamics Simulations , 2012 .

[41]  S. Baldelli,et al.  Sum frequency generation spectroscopy of the aqueous interface: Ionic and soluble molecular solutions , 2000 .

[42]  J. Sung,et al.  Fast Motion of the Surface Alcohol Molecules Deduced from Sum-Frequency Vibrational Spectroscopy , 2007 .