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Modeling the heme vibrational spectrum: Normal-mode analysis of nickel (II) etioporphyrin-I from resonance raman, ft-raman, and infrared spectra of multiple isotopomers
Songzhou Hu,
Arka Mukherjee,
Christine Piffat,
Ronald S. W. Mak,
Xiao-Yuan Li,
Thomas G. Spiro,
Songzhou Hu
Department of Chemistry, Princeton University, Princeton, New Jersey 08540
Search for more papers by this authorArka Mukherjee
Department of Chemistry, Princeton University, Princeton, New Jersey 08540
Search for more papers by this authorChristine Piffat
Department of Chemistry, Princeton University, Princeton, New Jersey 08540
Search for more papers by this authorRonald S. W. Mak
Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
Search for more papers by this authorXiao-Yuan Li
Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
Search for more papers by this authorCorresponding Author
Thomas G. Spiro
Department of Chemistry, Princeton University, Princeton, New Jersey 08540
Department of Chemistry, Princeton University, Princeton, New Jersey 08540Search for more papers by this authorSongzhou Hu,
Arka Mukherjee,
Christine Piffat,
Ronald S. W. Mak,
Xiao-Yuan Li,
Thomas G. Spiro,
Songzhou Hu
Department of Chemistry, Princeton University, Princeton, New Jersey 08540
Search for more papers by this authorArka Mukherjee
Department of Chemistry, Princeton University, Princeton, New Jersey 08540
Search for more papers by this authorChristine Piffat
Department of Chemistry, Princeton University, Princeton, New Jersey 08540
Search for more papers by this authorRonald S. W. Mak
Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
Search for more papers by this authorXiao-Yuan Li
Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
Search for more papers by this authorCorresponding Author
Thomas G. Spiro
Department of Chemistry, Princeton University, Princeton, New Jersey 08540
Department of Chemistry, Princeton University, Princeton, New Jersey 08540Search for more papers by this authorAbstract
Nearly complete vibrational assignments have been obtained for a heme model, nickel etioporphyrin-I (NiEPI), using variable-wavelength resonance Raman (RR), and FT-Raman (FT-R), as well as infrared (IR) spectroscopy, on a series of isotopomers labeled at positions in the skeleton (15N, β-13C, meso-d4, 15N-meso-d4) and in the peripheral substituents (methyl-d12, ethyl-d8, and ethyl-d12). The vibrational bands are assigned to the porphyrin skeletal and substituent modes on the basis of the mode description scheme developed for nickel octaethylporphyrin (NiOEP) with the aid of a normal-mode analysis of NiEPI, explicitly including the peripheral substituents, i.e., the methyl and ethyl groups. The previously reported NiOEP force field was refined to account for the observed isotope shifts of NiEPI isotopomers. An important result is the requirement of relatively large, long-range force constants for methine bridge bonds on opposite sides of the porphyrin ring. These 1–8 and 1–9 interaction force constants are required to reproduce the frequencies and isotope shifts of six Cα-Cm stretching modes and especially to predict the relative order of the two highest-frequency Eu modes, v(Cα-Cm) (v38, ∼ 1570 cm−1) and v(Cβ-Cβ) (v37, ∼ 1600 cm−1). Most of the substituent (methyl and ethyl) vibrations are located in the RR and IR spectra. Strong RR enhancement of some substituent modes can be attributed to hyperconjugative interaction of the aliphatic groups with the porphyrin a1u orbital, as well as vibrational mixing of substituent modes with the nearby skeletal modes. © 1995 John Wiley & Sons, Inc.
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