Electronic polarization effect on low-frequency infrared and Raman spectra of aprotic solvent: Molecular dynamics simulation study with charge response kernel by second order Møller-Plesset perturbation method

Miho Isegawa, Shigeki Kato

    Research output: Contribution to journalArticlepeer-review

    9 Citations (Scopus)

    Abstract

    Low-frequency infrared (IR) and depolarized Raman scattering (DRS) spectra of acetonitrile, methylene chloride, and acetone liquids are simulated via molecular dynamics calculations with the charge response kernel (CRK) model obtained at the second order Møller-Plesset perturbation (MP2) level. For this purpose, the analytical second derivative technique for the MP2 energy is employed to evaluate the CRK matrices. The calculated IR spectra reasonably agree with the experiments. In particular, the agreement is excellent for acetone because the present CRK model well reproduces the experimental polarizability in the gas phase. The importance of interaction induced dipole moments in characterizing the spectral shapes is stressed. The DRS spectrum of acetone is mainly discussed because the experimental spectrum is available only for this molecule. The calculated spectrum is close to the experiment. The comparison of the present results with those by the multiple random telegraph model is also made. By decomposing the polarizability anisotropy time correlation function to the contributions from the permanent, induced polarizability and their cross term, a discrepancy from the previous calculations is observed in the sign of permanent-induce cross term contribution. The origin of this discrepancy is discussed by analyzing the correlation functions for acetonitrile.

    Original languageEnglish
    Article number244502
    JournalJournal of Chemical Physics
    Volume127
    Issue number24
    DOIs
    Publication statusPublished - 2007

    All Science Journal Classification (ASJC) codes

    • Physics and Astronomy(all)
    • Physical and Theoretical Chemistry

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