Infrared Spectral Assignment of Pyrimidine and Pyrazine in the C-H Stretching Region by an Effective Spectroscopic Hamiltonian

Chakraborty, Shubhadip and Mukherjee, Sumanta and Mahapatra, Susanta and Das, Puspendu K (2018) Infrared Spectral Assignment of Pyrimidine and Pyrazine in the C-H Stretching Region by an Effective Spectroscopic Hamiltonian. In: VIBRATIONAL SPECTROSCOPY, 99 . pp. 196-203.

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Abstract

Mid-Infrared spectra of pyrimidine (PM) and pyrazine (PZ) were recorded in the gas phase using a multi-pass long path gas cell. The IR band structure of these compounds above and below 3000 cm(-1) is very broad and contains many humps and shoulders. These humps and shoulders are due to various higher quantum excitation of low-frequency vibrational modes, which participate in Fermi resonance with the nearby C-H stretch fundamentals and appears in this region. We constructed an Effective Spectroscopic Hamiltonian (ESH) in a mixed local mode (LM) normal mode (NM) basis to assign the various overtone and combination bands in the C-H stretching region of these compounds. The C-H stretching vibrations of both PZ and PM were treated as symmetrized anharmonic Morse oscillators in local coordinates and the in-plane deformations down to 1000 cm(-1) were treated as normal coordinates. The ESHs were diagonalized and the resulting eigenvalues were subsequently fitted in a given parameter space with the experimentally observed bands. The eigenvalues of the converged Hamiltonian are the anharmonic frequencies and the transition intensities were obtained by summing the squared eigenvector components. The overtone and combination transitions near 3000 cm(-1) of both PM and PZ were identified and assigned from the eigenvector coefficients of the ESH matrix. The wavefunctions of a pure C-H stretch, overtone of the H-C-C in-plane bend and due to Type 1 Fermi coupling (resonance between a fundamental with an overtones of a low frequency mode, in this case resonance between the C-H strech and the overtone of H-C-C in-plane bending modes) has been demonstrated pictorially.

Item Type:	Journal Article
Publication:	VIBRATIONAL SPECTROSCOPY
Publisher:	ELSEVIER SCIENCE BV
Additional Information:	Copyright of this article belong to ELSEVIER SCIENCE BV
Keywords:	IR spectra; Pyrazine and Pyrimidine; Fermi resonance; Local mode; Normal mode; Effective Spectroscopic Hamiltonian
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry Division of Physical & Mathematical Sciences > Mathematics
Date Deposited:	26 Dec 2018 05:46
Last Modified:	30 Dec 2018 13:10
URI:	http://eprints.iisc.ac.in/id/eprint/61314

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