TY - JOUR
T1 - Two-dimensional vibrational spectroscopy. I. Theoretical calculation of the nonlinear Raman response function of CHCl3
AU - Hahn, Sangjoon
AU - Park, Kisam
AU - Cho, Minhaeng
N1 - Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 1999/9/1
Y1 - 1999/9/1
N2 - The two-dimensional Raman response function of CHCl3 is theoretically considered with interpretations of each peak in terms of the associated vibrational transition pathways. In order to numerically calculate the 2D Raman spectrum, ab initio calculations of necessary quantities, such as the first- and second-order derivatives of the molecular polarizability with respect to vibrational coordinates and cubic potential anharmonic coefficients, were carried out by using the basis set 6-311 + + G(2df,2pd) at the Hartree-Fock level. Quantitative comparison between the two nonlinear response functions associated with the mechanical and electronic anharmonicities shows that the 2D Raman response from the high-frequency intramolecular vibrational modes of CHCl3 is mainly determined by the mechanical (potential) anharmonicity contributions. On the other hand, it is found that the two distinctive contributions originating from the mechanical and electronic anharmonicities interfere in the low-frequency region of the 2D spectrum. Overall, it is suggested that the high-frequency 2D Raman spectrum could provide a map of the mechanical anharmonic mode couplings. We briefly discuss how the 2D Raman spectrum can be used to elucidate the potential energy hypersurface and in turn to study the intramolecular vibrational energy redistribution process.
AB - The two-dimensional Raman response function of CHCl3 is theoretically considered with interpretations of each peak in terms of the associated vibrational transition pathways. In order to numerically calculate the 2D Raman spectrum, ab initio calculations of necessary quantities, such as the first- and second-order derivatives of the molecular polarizability with respect to vibrational coordinates and cubic potential anharmonic coefficients, were carried out by using the basis set 6-311 + + G(2df,2pd) at the Hartree-Fock level. Quantitative comparison between the two nonlinear response functions associated with the mechanical and electronic anharmonicities shows that the 2D Raman response from the high-frequency intramolecular vibrational modes of CHCl3 is mainly determined by the mechanical (potential) anharmonicity contributions. On the other hand, it is found that the two distinctive contributions originating from the mechanical and electronic anharmonicities interfere in the low-frequency region of the 2D spectrum. Overall, it is suggested that the high-frequency 2D Raman spectrum could provide a map of the mechanical anharmonic mode couplings. We briefly discuss how the 2D Raman spectrum can be used to elucidate the potential energy hypersurface and in turn to study the intramolecular vibrational energy redistribution process.
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U2 - 10.1063/1.479709
DO - 10.1063/1.479709
M3 - Article
AN - SCOPUS:0001143103
SN - 0021-9606
VL - 111
SP - 4121
EP - 4130
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 9
ER -