TY - JOUR
T1 - Electronic polarization effect on low-frequency infrared and Raman spectra of aprotic solvent
T2 - Molecular dynamics simulation study with charge response kernel by second order Møller-Plesset perturbation method
AU - Isegawa, Miho
AU - Kato, Shigeki
N1 - Funding Information:
We are grateful to Professor A. Morita, Dr. S. Iuchi, and Dr. S. Yamazaki for valuable discussions. This work was supported by the Grant-in-Aid for Scientific Research from the Ministry of Education and Science, Japan.
PY - 2007
Y1 - 2007
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=37549060722&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=37549060722&partnerID=8YFLogxK
U2 - 10.1063/1.2813421
DO - 10.1063/1.2813421
M3 - Article
C2 - 18163686
AN - SCOPUS:37549060722
VL - 127
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 24
M1 - 244502
ER -