Publication Abstracts

Ma et al. 2014

Ma, Q.-C., C. Boulet, and R.H. Tipping, 2014: Two dimensional symmetric correlation functions of the Ŝ operator and two dimensional Fourier transforms: Considering the line coupling for P and R lines of linear molecules. J. Chem. Phys., 140, no. 10, 104304, doi:10.1063/1.4867417.

The refinement of the Robert-Bonamy (RB) formalism by considering the line coupling for isotropic Raman Q lines of linear molecules developed in our previous study [Q. Ma, C. Boulet, and R. H. Tipping, J. Chem. Phys. 139, 034305 (2013)] has been extended to infrared P and R lines. In these calculations, the main task is to derive diagonal and off-diagonal matrix elements of the Liouville operator iS1—S2 introduced in the formalism. When one considers the line coupling for isotropic Raman Q lines where their initial and final rotational quantum numbers are identical, the derivations of off-diagonal elements do not require extra correlation functions of the Ŝ operator and their Fourier transforms except for those used in deriving diagonal elements. In contrast, the derivations for infrared P and R lines become more difficult because they require a lot of new correlation functions and their Fourier transforms. By introducing two dimensional correlation functions labeled by two tensor ranks and making variable changes to become even functions, the derivations only require the latters' two dimensional Fourier transforms evaluated at two modulation frequencies characterizing the averaged energy gap and the frequency detuning between the two coupled transitions. With the coordinate representation, it is easy to accurately derive these two dimensional correlation functions. Meanwhile, by using the sampling theory one is able to effectively evaluate their two dimensional Fourier transforms. Thus, the obstacles in considering the line coupling for P and R lines have been overcome. Numerical calculations have been carried out for the half-widths of both the isotropic Raman Q lines and the infrared P and R lines of C2H2 broadened by N2. In comparison with values derived from the RB formalism, new calculated values are significantly reduced and become closer to measurements.

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BibTeX Citation

@article{ma06900s,
  author={Ma, Q.-C. and Boulet, C. and Tipping, R. H.},
  title={Two dimensional symmetric correlation functions of the Ŝ operator and two dimensional Fourier transforms: Considering the line coupling for P and R lines of linear molecules},
  year={2014},
  journal={J. Chem. Phys.},
  volume={140},
  number={10},
  pages={104304},
  doi={10.1063/1.4867417},
}

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RIS Citation

TY  - JOUR
ID  - ma06900s
AU  - Ma, Q.-C.
AU  - Boulet, C.
AU  - Tipping, R. H.
PY  - 2014
TI  - Two dimensional symmetric correlation functions of the Ŝ operator and two dimensional Fourier transforms: Considering the line coupling for P and R lines of linear molecules
JA  - J. Chem. Phys.
VL  - 140
IS  - 10
SP  - 104304
DO  - 10.1063/1.4867417
ER  -

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