Abstract
The mid-infrared spectrum of aniline vapour is reinvestigated, and the IR spectrum of the compound in solid nitrogen matrix under a cryogenic condition is measured for the first time. A thorough assignment of many features of the vapour spectrum, particularly those related to amine inversion mode, is suggested. By use of PGOPHER fitting of the rotational band contours in the fingerprint region, the amine inversion tunnelling splitting at v = 1 level of NH2 scissoring and C–N bending vibrations in the vapour spectrum are identified. Our analysis reveals that excitation of one quantum of NH2 scissoring results in lowering of the tunnelling barrier, whereas, the barrier is increased upon excitation of the C–N bending. Comparison of the spectra recorded in nitrogen and argon matrixes reveal that the former hinders the NH2 inversion and consequently, transitions corresponding to higher quanta of this mode are absent.
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N W Larsen, L L Hansen and F M Nicolaisen Chem. Phys. Lett. 43 584 (1976)
R A Kydd and P J Krueger Chem. Phys. Lett. 49 539 (1977)
T Cvita, J M Hollas and G H Kirby Mol. Phys. 19 305 (1970)
J M Hollas, M R Howson, T Ridley and L Halonen Chem. Phys. Lett. 98 611 (1983)
W E Sinclair and D W Pratt J. Chem. Phys. 105 7942 (1996)
X Song, M Yang, E R Davidson and J P Reilly J. Chem. Phys. 99 2334 (1993)
H Piest, G V Helden and G Meijer J. Chem. Phys. 110 2010 (1999)
K Sugawara, J Miyawaki, T Nakanaga, H Takeo, G Lembach, S Djafari, H-D Barth and B Brutschy J. Phys. Chem. 100 17145 (1996)
M R Nimlos, M A Young, E R Bernstein and D F Kelly J. Chem. Phys. 91 5268 (1989)
T Nakanaga and F Ito J. Phys. Chem. A 103 5440 (1999)
Y Hu and E R Bernstein J. Phys. Chem. A. 113 639 (2009)
R A Kydd and P J Krueger J. Chem. Phys. 69 827 (1978)
S Yan and L H Spangler J. Chem. Phys. 96 4106 (1992)
M Becucci. E Castellucci, I Lόpez-Tocόn, G Pietraperzia, P R Salvi and W Caminati J. Phys. Chem. A 103 8946 (1999)
M Honda, A Fuji, E Fujimaki, T Ebata and N Mikami J. Phys. Chem. A 107 3678 (2003)
C Gee, S Douin, C Crepin and P Brechignac Chem. Phys. Lett. 338 130 (2001)
P M Wojciechowski, W Zierkiewicz, D Michalska and P Hobza J. Chem. Phys. 118 10900 (2003) and references therein
M Quack and M Stockburger J. Mol. Spectrosc. 43 87 (1972)
J C Evans Spectrochim. Acta 16 428 (1960)
Y Yamada, J-i Okano and N Mikami J. Chem. Phys. 123 124316 (2005)
B Fehrensen, D Luckhaus and M Quack Zeits. Phys. Chem. 209 1 (1999)
C M Western PGOPHER, A Program for Simulating Rotational Structure(University of Bristol), http://pgopher.chm.bris.ac.uk (2007)
M J Frisch, G W Trucks, H B Schlegel et al GAUSSIAN 03, Revision B.05 (Pittsburgh, PA: Gaussian Inc.) (2003)
G C Pimentel, M O Bulanin and M V Thiel J. Chem. Phys. 36 500 (1962)
G Herzberg Molecular Spectra and Molecular Structure, Part II, Infrared and Raman Spectra of Polyatomic Molecules (New York: D. Van Nostrand Company) (1945)
E Catalano and D E Milligan J. Chem. Phys. 30 45 (1959)
T N Wassermann, D Luckhaus, S Coussan and M A Suhm Phys. Chem. Chem. Phys. 8 2344 (2006)
S Lopes, A V Domanskaya, R Fausto, M Räsänen and L Khriachtchev J. Chem. Phys. 133 144507 (2010)
Acknowledgments
The authors acknowledge the financial support received from the Council of Scientific and Industrial Research (CSIR), Govt. of India to carryout the research reported here. BB thanks the CSIR for the SRF grants.
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Mukherjee, M., Bandyopadhyay, B., Biswas, P. et al. Amine inversion effects on the IR spectra of aniline in the gas phase and cold inert gas matrixes. Indian J Phys 86, 201–208 (2012). https://doi.org/10.1007/s12648-012-0037-y
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DOI: https://doi.org/10.1007/s12648-012-0037-y