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Nitrobenzene anti-parallel dimer formation in non-polar solvents
1. C. Dorosh, Białkowska-E. Jaworska, Z. Kisiel, and L. Pszczółkwski, “New measurements and global analysis of rotational spectra of Cl-, Br-, and I-benzene: spectroscopic constants and electric dipole moments,” J. Mol.Spectrosc. 246, 228–232 (2007).
2. D. R. Borst, T. M. Korter, and D. W. Pratt, “On the additivity of bond dipole moments. Stark effect studies of the rotationally resolved electronic spectra of aniline, benzonitrile, and aminobenzonitrile,” Chem. Phys. Lett. 350, 485–490 (2001).
3. R. D. Nelson Jr., D. R. Lide Jr., and A. A. Maryott, “Selected Values of Electric Dipole Moments for Molecules in the Gas Phase (National Standard Reference Data-National Bureau of Standard 10; U. S. Government Printing Office, Washington, D.C., 1967), p. 31.
4. T. Shikata, N. Sugimoto, Y. Sakai, and J. Watanabe, “Dimeric molecular association of dimethyl sulfoxide in solutions of nonpolar liquids,” J. Phys. Chem. B 116, 12605–12613 (2012).
5. T. Shikata and N. Yoshida, “Dielectric behaviors of typical benzene monosubstitutes, bromobenzene and benzonitrile,” J. Phys. Chem. A 116, 4735–4744 (2012).
6. T. Shikata and N. Sugimoto, “Reconsideration of the anomalous dielectric behavior of dimethyl sulfoxide in the pure liquid state,” Phys. Chem. Chem. Phys. 13, 16542–16547 (2011).
7. T. Shikata and N. Sugimoto, “Dimeric molecular association of dimethyl sulfoxide in solutions of nonpolar liquids,” J.Phys. Chem. A 116, 990–999 (2012).
8. D. R. Bauer, G. R. Alms, J. I. Brauman, and R. Pecora, “Depolarized rayleigh scattering and 13C NMR studies of anisotropic molecular reorientation of aromatic compounds in solution,” J. Chem. Phys. 61, 2255–2261 (1974).
9. S. Kinoshita, Y. Kai, M. Yamaguchi, and T. Yagi, “Direct comparison of femtosecond fourier-transform raman spectrum with spontaneous light scattering spectrum,” Chem. Phys. Lett. 236, 259–264 (1995).
10. V. V. Daniel, Dielectric Relaxation (Acedemic Press, London, 1967), Chap. 7 and 8.
11. G. Herzberg, Molecular Spectra and Structure II, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand Reinhold, New York, 1945).
12. R. M. Weiner, Introduction to Bose–Einstein Correlations and Subatomic Interferometry (John Wiley, 2000).
13. R. H. Wright, “Odor and molecular vibration: response to nitrobenzne-d5 of honey bees (Apis Mellifera L.) conditioned with nitrobenzene,” Experientia 31, 530 (1975).
14. J. E. Pedersen and S. R. Keiding, “THz time-domain spectroscopy of nonpolar liquids,” IEEE J. Quantum Electron. 28, 2518–2522 (1992).
15. J. K. Vij, T. Grochulski, A. Kocot, and F. Hufnagel, “Complex permittivity measurements of acetone in the frequency region 50–310GHz,” Mol. Phys. 72, 353–361 (1991).
16. J. K. Vij and F. Hufnagel, “Dielectric relaxation and libration spectroscopy of some aliphatic ketones and their molecular behavior,” J. Phys. Chem. 95, 6142–6148 (1991).
17. F. Marchesoni, J. K. Vij, and W. T. Coffey, “Nonlinear budó model for dielectric relaxation: comparison with new experimental data,” Zeitschrift Phys. B, Condensed Matter 61, 357–366 (1985).
18. P. Debye, “Einige resultate einer kinetischen theorie der isolatoren,” Phys. Zeit. 13, 97–100 (1912).
19. H. Fröhlich, Theory of Dielectrics. 2nd ed. (Oxford Univ. Press, London, 1958).
21. G. Oster and J. G. Kirkwood, “The influence of hindered molecular rotation on the dielectric constants of water, alcohols, and other polar liquids,” J. Chem. Phys. 11, 175–178 (1943).
23. T. Chakraborty and S. N. Rai, “Depolarization ratio and correlation between the relative intensity data and the abundance ratio of various isotopes of liquid carbon tetrachloride at room temperature,” Spectrochim. Acta Part A 62, 438–445 (2005).
24. Y. Amo and Y. Tominaga, “Low-frequency raman scattering of liquid CCl4, CHCl3, and Acetone,” J. Chem. Phys. 109, 3994–39998 (1998).
26. R. W. Taft, G. B. Klingensmith, and S. Ehrenson, “Multipolar complexes. I. The dimerization of nitrobenzene1,” J. Am. Chem. Soc. 87, 3620–3626 (1965).
27. G. R. Alms, D. R. Bauer, J. I. Brauman, and R. Pecora, “Depolarized rayleigh scattering and orientational relaxation of molecules in solution. II chloroform and nitrobenzene,” J. Chem. Phys. 59, 5310–5320 (1973).
28. S. J. Bertucci, A. K. Burnham, G. R. Alms, and W. H. Flygare, “Light scattering studies of orientational pair correlations in liquids composed of anisometric molecules,” J. Chem. Phys. 66, 605–616 (1977).
29. S. Tsuzuki, K. Honda, T. Uchimaru, and M. Mikami, “Intermolecular interactions of nitrobenzene-benzene complex and nitrobenzene dimer: significant stabilization of slipped-parallel orientation by dispersion interaction,” J. Chem. Phys. 125, 124304 (2006).
30. M. Katayama, S. Ashiki, T. Amakasu, and K. Ozutsumi, “Liquid structure of benzene and its derivatives as studied by means of X-ray scattering,” Phys. Chem. Liq. 48, 797–809 (2010).
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We investigated the dielectric and depolarized Rayleigh scattering behaviors of nitrobenzene (NO2-Bz), which is a benzene mono-substituted with a planar molecular frame bearing the large electric dipole moment 4.0 D, in non-polar solvents solutions, such as tetrachloromethane and benzene, at up to 3 THz for the dielectric measurements and 8 THz for the scattering experiments at 20 °C. The dielectric relaxation strength of the system was substantially smaller than the proportionality to the concentration in a concentrated regime and showed a Kirkwood correlation factor markedly lower than unity; g K ∼ 0.65. This observation revealed that NO2-Bz has a tendency to form dimers, (NO2-Bz)2, in anti-parallel configurations for the dipole moment with increasing concentration of the two solvents. Both the dielectric and scattering data exhibited fast and slow Debye-type relaxation modes with the characteristic time constants ∼7 and ∼50 ps in a concentrated regime (∼15 and ∼30 ps in a dilute regime), respectively. The fast mode was simply attributed to the rotational motion of the (monomeric) NO2-Bz. However, the magnitude of the slow mode was proportional to the square of the concentration in the dilute regime; thus, the mode was assigned to the anti-parallel dimer, (NO2-Bz)2, dissociation process, and the slow relaxation time was attributed to the anti-parallel dimer lifetime. The concentration dependencies of both the dielectric and scattering data show that the NO2-Bz molecular processes are controlled through a chemical equilibrium between monomers and anti-parallel dimers, 2NO2-Bz ↔ (NO2-Bz)2, due to a strong dipole-dipole interaction between nitro groups.
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