Orientational Pair Correlations in a Dipolar Molecular Liquid: Time-Resolved Resonant and Nonresonant Pump–Probe Spectroscopies

Yamada, Steven A.; Bailey, Heather E.; Fayer, Michael D.

doi:10.1021/acs.jpcb.8b10711

Title: Orientational Pair Correlations in a Dipolar Molecular Liquid: Time-Resolved Resonant and Nonresonant Pump–Probe Spectroscopies

Journal Article · Fri Nov 09 00:00:00 UTC 2018 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI: https://doi.org/10.1021/acs.jpcb.8b10711 · OSTI ID:1787011

^[1]; Bailey, Heather E. ^[2];

^[2]

Stanford Univ., CA (United States); Stanford University, Dept. of Chemistry
Stanford Univ., CA (United States)

Orientational pair correlations (OPCs), when they are sufficiently strong in a liquid, contain information on the interplay between structure and dynamics that arise from intermolecular interactions. Consequently, the quantification of OPCs remains a subject of substantial interest in current experimental and theoretical work. In the case of benzonitrile, the importance of OPCs remains ambiguous owing to the use of model-dependent analyses or reliance on a single spectroscopic technique. In this work, IR polarization selective pump-probe (PSPP) and optical heterodyne-detected optical Kerr effect (OHD-OKE) experiments were used to quantify OPCs in benzonitrile. These methods measure single molecule and collective relaxation, respectively. Comparison of the orientational correlation function (PSPP) of the naturally abundant 13CN stretching mode and the polarizability anisotropy relaxation (OHD-OKE) of the liquid revealed that collective reorientation was a factor of 1.56 ± 0.08 slower than the single molecule reorientation time. The two types of measurements on dilute benzonitrile in carbon tetrachloride were the same within experimental error. These results support the proposition that OPCs exist and arise from the formation of parallel-aligned intermolecular structures in the neat liquid.

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Research Organization:: Stanford Univ., CA (United States)

Sponsoring Organization:: US Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-84ER13251

OSTI ID:: 1787011

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Issue: 50 Vol. 122; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (49)

Depolarized Rayleigh Scattering: Reorientational Motion and Orientational Correlations in Acetonitrile and Carbon Disulfide Versmold, H. Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 82, Issue 5 https://doi.org/10.1002/bbpc.197800085	journal	May 1978
Time-dependent fluorescence depolarization and Brownian rotational diffusion coefficients of macromolecules Tao, Terence Biopolymers, Vol. 8, Issue 5 https://doi.org/10.1002/bip.1969.360080505	journal	November 1969
Viscosities and thermodynamics of viscous flow of some binary mixtures at different temperatures Acevedo, Ines L.; Katz, Miguel Journal of Solution Chemistry, Vol. 19, Issue 10 https://doi.org/10.1007/bf00650507	journal	October 1990
Electrons weakly bound to molecules by dipolar, quadrupolar or polarization forces Abdoul-Carime, H.; Desfrançois, C. The European Physical Journal D, Vol. 2, Issue 2 https://doi.org/10.1007/pl00021568	journal	June 1998
Polarized fluorescence and rotational brownian motion Ehrenberg, M.; Rigler, R. Chemical Physics Letters, Vol. 14, Issue 5 https://doi.org/10.1016/0009-2614(72)87202-6	journal	July 1972
Precise dipole moment and quadrupole coupling constants of benzonitrile Wohlfart, Kirstin; Schnell, Melanie; Grabow, Jens-Uwe Journal of Molecular Spectroscopy, Vol. 247, Issue 1 https://doi.org/10.1016/j.jms.2007.10.006	journal	January 2008
A theory of fluorescence polarization decay in membranes Kinosita, K.; Kawato, S.; Ikegami, A. Biophysical Journal, Vol. 20, Issue 3 https://doi.org/10.1016/s0006-3495(77)85550-1	journal	December 1977
Effect of librational motion on fluorescence depolarization and nuclear magnetic resonance relaxation in macromolecules and membranes Lipari, G.; Szabo, A. Biophysical Journal, Vol. 30, Issue 3 https://doi.org/10.1016/s0006-3495(80)85109-5	journal	June 1980
Densities and Viscosities of Binary Liquid Mixtures of Anisole or Methyl tert -Butyl Ether with Benzene, Chlorobenzene, Benzonitrile, and Nitrobenzene Viswanathan, S.; Anand Rao, M.; Prasad, D. H. L. Journal of Chemical & Engineering Data, Vol. 45, Issue 5 https://doi.org/10.1021/je990288b	journal	September 2000
Molecular Dynamics Study of Polarizability Anisotropy Relaxation in Aromatic Liquids and Its Connection with Local Structure Elola, M. Dolores; Ladanyi, Branka M. The Journal of Physical Chemistry B, Vol. 110, Issue 31 https://doi.org/10.1021/jp062071b	journal	August 2006
Orientational Dynamics of Room Temperature Ionic Liquid/Water Mixtures: Water-Induced Structure Sturlaugson, Adam L.; Fruchey, Kendall S.; Fayer, Michael D. The Journal of Physical Chemistry B, Vol. 116, Issue 6 https://doi.org/10.1021/jp209942r	journal	February 2012
Dielectric Behaviors of Typical Benzene Monosubstitutes, Bromobenzene and Benzonitrile Shikata, Toshiyuki; Sugimoto, Natsuki; Sakai, Yuji The Journal of Physical Chemistry B, Vol. 116, Issue 41 https://doi.org/10.1021/jp308037n	journal	October 2012
Polarizability Anisotropy Relaxation in Nanoconfinement: Molecular Simulation Study of Acetonitrile in Silica Pores Milischuk, Anatoli A.; Ladanyi, Branka M. The Journal of Physical Chemistry B, Vol. 117, Issue 49 https://doi.org/10.1021/jp4064615	journal	September 2013
Dynamics in the Isotropic Phase of Nematogens Using 2D IR Vibrational Echo Measurements on Natural-Abundance ¹³ CN and Extended Lifetime Probes Sokolowsky, Kathleen P.; Fayer, Michael D. The Journal of Physical Chemistry B, Vol. 117, Issue 48 https://doi.org/10.1021/jp4071955	journal	November 2013
Orientational Dynamics in a Lyotropic Room Temperature Ionic Liquid Sturlaugson, Adam L.; Arima, Aaron Y.; Bailey, Heather E. The Journal of Physical Chemistry B, Vol. 117, Issue 47 https://doi.org/10.1021/jp407325b	journal	November 2013
Assessing Polarizability Models for the Simulation of Low-Frequency Raman Spectra of Benzene Bender, John S.; Coasne, Benoit; Fourkas, John T. The Journal of Physical Chemistry B, Vol. 119, Issue 29 https://doi.org/10.1021/jp509968v	journal	September 2014
Ultrafast Dynamics of Polar Monosubstituted Benzene Liquids Studied by the Femtosecond Optical Kerr Effect Smith, Neil A.; Meech, Stephen R. The Journal of Physical Chemistry A, Vol. 104, Issue 18 https://doi.org/10.1021/jp993170a	journal	May 2000
Transient birefringence of liquids induced by terahertz electric-field torque on permanent molecular dipoles Sajadi, Mohsen; Wolf, Martin; Kampfrath, Tobias Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14963	journal	April 2017
Isotropic and anisotropic Raman scattering from molecular liquids measured by spatially masked optical Kerr effect spectroscopy Fecko, C. J.; Eaves, J. D.; Tokmakoff, A. The Journal of Chemical Physics, Vol. 117, Issue 3 https://doi.org/10.1063/1.1485070	journal	July 2002
Effects of Anisotropic Molecular Rotational Diffusion on Nuclear Magnetic Relaxation in Liquids Huntress, Wesley T. The Journal of Chemical Physics, Vol. 48, Issue 8 https://doi.org/10.1063/1.1669645	journal	April 1968
Depolarized Light Scattering: Theory of the Sharp and Broad Rayleigh Lines Keyes, Thomas; Kivelson, Daniel The Journal of Chemical Physics, Vol. 56, Issue 3 https://doi.org/10.1063/1.1677267	journal	February 1972
Theory of Fluorescence Depolarization by Anisotropic Rotational Diffusion Chuang, T. J.; Eisenthal, K. B. The Journal of Chemical Physics, Vol. 57, Issue 12 https://doi.org/10.1063/1.1678194	journal	December 1972
Depolarized Rayleigh scattering and orientational relaxation of molecules in solution. II Chloroform and nitrobenzene Alms, G. R.; Bauer, D. R.; Brauman, J. I. The Journal of Chemical Physics, Vol. 59, Issue 10 https://doi.org/10.1063/1.1679875	journal	November 1973
Polarizability response in polar solvents: Molecular-dynamics simulations of acetonitrile and chloroform Elola, M. Dolores; Ladanyi, Branka M. The Journal of Chemical Physics, Vol. 122, Issue 22 https://doi.org/10.1063/1.1925275	journal	June 2005
A mode coupling theory description of the short- and long-time dynamics of nematogens in the isotropic phase Li, Jie; Cang, Hu; Andersen, Hans C. The Journal of Chemical Physics, Vol. 124, Issue 1 https://doi.org/10.1063/1.2145679	journal	January 2006
Dynamic orientational pair correlations in symmetric tops and static orientational pair correlations in anisometric molecules Gierke, T. D. The Journal of Chemical Physics, Vol. 65, Issue 10 https://doi.org/10.1063/1.432904	journal	November 1976
Light scattering studies of transverse sound wave and molecular motion in benzonitrile Whittenburg, S. L.; Wang, C. H. The Journal of Chemical Physics, Vol. 66, Issue 11 https://doi.org/10.1063/1.433802	journal	June 1977
Light scattering studies of orientational pair correlations in liquids composed of anisometric molecules Bertucci, Sidney J.; Burnham, A. K.; Alms, G. R. The Journal of Chemical Physics, Vol. 66, Issue 2 https://doi.org/10.1063/1.433983	journal	January 1977
Depolarized Rayleigh scattering from benzonitrile Alms, G. R.; Patterson, G. D. The Journal of Chemical Physics, Vol. 68, Issue 8 https://doi.org/10.1063/1.436251	journal	April 1978
Comment on ’’Depolarized Rayleigh spectroscopy from benzonitrile’’ Whittenburg, S. L.; Wang, C. H. The Journal of Chemical Physics, Vol. 71, Issue 1 https://doi.org/10.1063/1.438143	journal	July 1979
Molecular dynamics studies of orientational and collision‐induced light scattering in molecular fluids Frenkel, D.; McTague, J. P. The Journal of Chemical Physics, Vol. 72, Issue 4 https://doi.org/10.1063/1.439429	journal	February 1980
Anisotropic reorientational relaxation of biphenyl: Transient grating optical Kerr effect measurements Deeg, F. W.; Stankus, John J.; Greenfield, S. R. The Journal of Chemical Physics, Vol. 90, Issue 12 https://doi.org/10.1063/1.456264	journal	June 1989
Interaction‐induced contributions to polarizability anisotropy relaxation in polar liquids Ladanyi, Branka M.; Liang, Ying Q. The Journal of Chemical Physics, Vol. 103, Issue 15 https://doi.org/10.1063/1.470413	journal	October 1995
Orientational correlation functions and polarization selectivity for nonlinear spectroscopy of isotropic media. I. Third order Tokmakoff, A. The Journal of Chemical Physics, Vol. 105, Issue 1 https://doi.org/10.1063/1.471856	journal	July 1996
Comparisons of 2D IR measured spectral diffusion in rotating frames using pulse shaping and in the stationary frame using the standard method Karthick Kumar, S. K.; Tamimi, A.; Fayer, M. D. The Journal of Chemical Physics, Vol. 137, Issue 18 https://doi.org/10.1063/1.4764470	journal	November 2012
Polarizability anisotropy relaxation in nanoconfinement: Molecular simulation study of water in cylindrical silica pores Milischuk, Anatoli A.; Ladanyi, Branka M. The Journal of Chemical Physics, Vol. 141, Issue 18 https://doi.org/10.1063/1.4896218	journal	November 2014
Water-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulations Yamada, Steven A.; Thompson, Ward H.; Fayer, Michael D. The Journal of Chemical Physics, Vol. 146, Issue 23 https://doi.org/10.1063/1.4984766	journal	June 2017
Microscopic theory of collective anisotropic molecular reorientation Keyes, T. Molecular Physics, Vol. 23, Issue 4 https://doi.org/10.1080/00268977200100731	journal	April 1972
RISM calculation of the structure of liquid acetonitrile Hsu, C. S.; Chandler, D. Molecular Physics, Vol. 36, Issue 1 https://doi.org/10.1080/00268977800101521	journal	July 1978
Infrared, Raman and microwave studies of the molecular dynamics and interactions in liquid benzonitrile Guillaume, F.; Yarwood, J.; Price, A. H. Molecular Physics, Vol. 62, Issue 6 https://doi.org/10.1080/00268978700102991	journal	December 1987
The mode coupling theory of structural relaxations Götze, W.; Sjögren, L. Transport Theory and Statistical Physics, Vol. 24, Issue 6-8 https://doi.org/10.1080/00411459508203936	journal	July 1995
Optically-heterodyne-detected optical Kerr effect (OHD-OKE): Applications in condensed phase dynamics Smith, Neil A.; Meech, Stephen R. International Reviews in Physical Chemistry, Vol. 21, Issue 1 https://doi.org/10.1080/01442350110092701	journal	January 2002
Theory of the Rotational Brownian Motion of a Free Rigid Body Favro, L. Dale Physical Review, Vol. 119, Issue 1 https://doi.org/10.1103/physrev.119.53	journal	July 1960
Intermolecular and diffusive dynamics of pure acetonitrile isotopomers studied by depolarized Rayleigh scattering and femtosecond optical kerr effect Foggi, P.; Bartolini, P.; Bellini, M. The European Physical Journal D, Vol. 21, Issue 2 https://doi.org/10.1140/epjd/e2002-00202-4	journal	November 2002
Fundamental aspects of light scattering and optical Kerr effect spectroscopy: From basic phenomena to non-quantum behaviors Kinoshita, S.; Sakai, Y.; Miyazaki, J. The European Physical Journal Special Topics, Vol. 209, Issue 1 https://doi.org/10.1140/epjst/e2012-01631-2	journal	June 2012
Transport, Collective Motion, and Brownian Motion Mori, Hazime Progress of Theoretical Physics, Vol. 33, Issue 3 https://doi.org/10.1143/ptp.33.423	journal	March 1965
Light Scattering Studies of Molecular Liquids Kivelson, D.; Madden, P. A. Annual Review of Physical Chemistry, Vol. 31, Issue 1 https://doi.org/10.1146/annurev.pc.31.100180.002515	journal	October 1980
Polarization selective spectroscopy experiments: methodology and pitfalls Tan, Howe-Siang; Piletic, Ivan R.; Fayer, M. D. Journal of the Optical Society of America B, Vol. 22, Issue 9 https://doi.org/10.1364/josab.22.002009	journal	January 2005
The Liquid Structure of Various Nitriles and N,N -Dimethylformamide Studied by the X-Ray Diffraction Method Using a CCD Detector Katayama, Misaki; Komori, Kohei; Ozutsumi, Kazuhiko Zeitschrift für Physikalische Chemie, Vol. 218, Issue 6-2004 https://doi.org/10.1524/zpch.218.6.659.33452	journal	June 2004

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Title: Orientational Pair Correlations in a Dipolar Molecular Liquid: Time-Resolved Resonant and Nonresonant Pump–Probe Spectroscopies

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