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Volume 212, 2018
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Teaching vibrational spectra to assign themselves

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A new paradigm for assigning vibrational spectra is described. Instead of proceeding from potential to Hamiltonian to eigenvalues/eigenvectors/intensities to spectrum, the new method goes “backwards” directly from spectrum to eigenvectors. The eigenvectors then “assign” the spectrum, in that they identify the basis states that contribute to each eigenvalue. To start, we demonstrate an algorithm that can obtain useful estimates of the eigenvectors connecting a real, symmetric Hamiltonian to its eigenvalues even if the only available information about the Hamiltonian is its diagonal elements. When this algorithm is augmented with information about transition intensities, it can be used to assign a complex vibrational spectrum using only information about (1) eigenvalues (the peak centers of the spectrum) and (2) a harmonic basis set (taken to be the diagonal elements of the Hamiltonian). Examples will be discussed, including application to the vibrationally complex spectral region of the formic acid dimer.

Graphical abstract: Teaching vibrational spectra to assign themselves

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The article was received on 13 Apr 2018, accepted on 21 May 2018 and first published on 21 May 2018

Article type: Paper
DOI: 10.1039/C8FD00075A
Citation: Faraday Discuss., 2018,212, 65-82

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    Teaching vibrational spectra to assign themselves

    Paul L. Houston, B. L. Van Hoozen, C. Qu, Q. Yu and J. M. Bowman, Faraday Discuss., 2018, 212, 65
    DOI: 10.1039/C8FD00075A

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