The changes in the vibrational properties of the peptide group upon formation of and halogen bonds are studied theoretically. Calculations are carried out for complexes of -methylacetamide (NMA), a well known model molecule of the peptide group, with halogen-containing molecules. For comparison, calculations are also carried out for some NMA–water hydrogen-bonding complexes. It is shown that the infrared (IR) intensity of the amide I mode of the peptide group is enhanced significantly (up to about or 2.6 times) upon halogen-bond formation, in spite of rather modest magnitudes of the intermolecular electric field and of the changes in the bond length and in the amide I vibrational frequency as compared with the cases of the hydrogen bonding. From the analysis of the changes in the dipole derivative and in the electronic structure, it is shown that this IR intensity enhancement arises from the intermolecular charge flux. For the halogen bonding complexes, some characteristic changes in the vibrational properties are seen, among which the IR intensity enhancement of the ND out-of-plane wagging mode is most notable. The reason why such large IR intensity enhancements are seen for these particular vibrational modes is examined.
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21 July 2010
Research Article|
July 15 2010
Intermolecular charge flux as the origin of infrared intensity enhancement upon halogen-bond formation of the peptide group
Hajime Torii
Hajime Torii
a)
Department of Chemistry, School of Education,
Shizuoka University
, 836 Ohya, Shizuoka 422-8529, Japan
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Tel./FAX: +81-54-238-4624. Electronic mail: torii@ed.shizuoka.ac.jp.
J. Chem. Phys. 133, 034504 (2010)
Article history
Received:
February 25 2010
Accepted:
June 02 2010
Citation
Hajime Torii; Intermolecular charge flux as the origin of infrared intensity enhancement upon halogen-bond formation of the peptide group. J. Chem. Phys. 21 July 2010; 133 (3): 034504. https://doi.org/10.1063/1.3456183
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