Direct calculations of mid- and near-IR absorption and circular dichroism spectra of chiral molecules using QM/MM molecular dynamics simulation method

Jun Ho Choi, Minhaeng Cho

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

The infrared (IR) and vibrational circular dichroism (VCD) spectra of (1S)-(-)-β-pinene in the mid- and near- IR frequency regions are numerically simulated by using a time-correlation function theory and mixed quantum/classical simulation method. Anharmonic vibrational dynamics and fluctuating atomic partial charges of the chiral pinene were obtained by carrying out quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations. Thus obtained time-correlation functions of electric and magnetic dipole moments are used to calculate the IR absorption and VCD spectra, and they are directly compared with experimental results. Not only the fundamental transition bands but also first overtone and combination bands in the near-IR frequency region are successfully simulated. It is shown that the polarizable nature of the solute is particularly important in quantitatively reproducing the near-IR spectra, whereas such polarization effects on dipole and rotational strengths of lower-frequency and large-amplitude vibrations are less critical. We anticipate that the present QM/MM MD method in combination with mixed quantum/classical time-correlation function theory to calculate both mid- and near-IR absorption and VCD spectra will be of critical use in interpreting vibrational optical activity properties of even conformationally flexible chiral molecules, such as proteins.

Original languageEnglish
Pages (from-to)4097-4103
Number of pages7
JournalJournal of Chemical Theory and Computation
Volume7
Issue number12
DOIs
Publication statusPublished - 2011 Dec 13

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Infrared absorption
Dichroism
infrared absorption
dichroism
Molecular dynamics
infrared spectra
molecular dynamics
Infrared radiation
Molecules
Computer simulation
absorption spectra
molecules
simulation
optical activity
Electric dipole moments
magnetic dipoles
electric dipoles
solutes
dipole moments
magnetic moments

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications

Cite this

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abstract = "The infrared (IR) and vibrational circular dichroism (VCD) spectra of (1S)-(-)-β-pinene in the mid- and near- IR frequency regions are numerically simulated by using a time-correlation function theory and mixed quantum/classical simulation method. Anharmonic vibrational dynamics and fluctuating atomic partial charges of the chiral pinene were obtained by carrying out quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations. Thus obtained time-correlation functions of electric and magnetic dipole moments are used to calculate the IR absorption and VCD spectra, and they are directly compared with experimental results. Not only the fundamental transition bands but also first overtone and combination bands in the near-IR frequency region are successfully simulated. It is shown that the polarizable nature of the solute is particularly important in quantitatively reproducing the near-IR spectra, whereas such polarization effects on dipole and rotational strengths of lower-frequency and large-amplitude vibrations are less critical. We anticipate that the present QM/MM MD method in combination with mixed quantum/classical time-correlation function theory to calculate both mid- and near-IR absorption and VCD spectra will be of critical use in interpreting vibrational optical activity properties of even conformationally flexible chiral molecules, such as proteins.",
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T1 - Direct calculations of mid- and near-IR absorption and circular dichroism spectra of chiral molecules using QM/MM molecular dynamics simulation method

AU - Choi, Jun Ho

AU - Cho, Minhaeng

PY - 2011/12/13

Y1 - 2011/12/13

N2 - The infrared (IR) and vibrational circular dichroism (VCD) spectra of (1S)-(-)-β-pinene in the mid- and near- IR frequency regions are numerically simulated by using a time-correlation function theory and mixed quantum/classical simulation method. Anharmonic vibrational dynamics and fluctuating atomic partial charges of the chiral pinene were obtained by carrying out quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations. Thus obtained time-correlation functions of electric and magnetic dipole moments are used to calculate the IR absorption and VCD spectra, and they are directly compared with experimental results. Not only the fundamental transition bands but also first overtone and combination bands in the near-IR frequency region are successfully simulated. It is shown that the polarizable nature of the solute is particularly important in quantitatively reproducing the near-IR spectra, whereas such polarization effects on dipole and rotational strengths of lower-frequency and large-amplitude vibrations are less critical. We anticipate that the present QM/MM MD method in combination with mixed quantum/classical time-correlation function theory to calculate both mid- and near-IR absorption and VCD spectra will be of critical use in interpreting vibrational optical activity properties of even conformationally flexible chiral molecules, such as proteins.

AB - The infrared (IR) and vibrational circular dichroism (VCD) spectra of (1S)-(-)-β-pinene in the mid- and near- IR frequency regions are numerically simulated by using a time-correlation function theory and mixed quantum/classical simulation method. Anharmonic vibrational dynamics and fluctuating atomic partial charges of the chiral pinene were obtained by carrying out quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations. Thus obtained time-correlation functions of electric and magnetic dipole moments are used to calculate the IR absorption and VCD spectra, and they are directly compared with experimental results. Not only the fundamental transition bands but also first overtone and combination bands in the near-IR frequency region are successfully simulated. It is shown that the polarizable nature of the solute is particularly important in quantitatively reproducing the near-IR spectra, whereas such polarization effects on dipole and rotational strengths of lower-frequency and large-amplitude vibrations are less critical. We anticipate that the present QM/MM MD method in combination with mixed quantum/classical time-correlation function theory to calculate both mid- and near-IR absorption and VCD spectra will be of critical use in interpreting vibrational optical activity properties of even conformationally flexible chiral molecules, such as proteins.

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