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Density Functional Theory Study of Red‐shifted Hydrogen Bonds of 4‐Pyridinemethanol with Water
Author(s) -
LI Quan,
CAI Jing,
CHEN JunRong,
ZHAO KeQing
Publication year - 2008
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.200890050
Subject(s) - chemistry , hydrogen bond , intermolecular force , monomer , density functional theory , basis set , molecule , computational chemistry , crystallography , natural bond orbital , polymer , organic chemistry
The hydrogen bonds of 1:1 and 1:2 complexes formed between 4‐pyridinemethanol and water have been investigated using a density functional theory (DFT) method and 6‐311++G∗ ∗ basis set, and three and eight stable geometries have been obtained for 1:1 and 1:2 complexes, respectively. The interaction energy is −20.536 and −44.256 kJ/mol for the most stable 1:1 and 1:2 complexes, respectively, after the basis set superposition error and zero‐point corrections. The formation of OH···N(O) hydrogen bonds makes OH symmetric stretching modes in the complexes red‐shifted relative to those of the monomer. The natural bond orbit analysis indicates that the intermolecular charge transfer between 4‐pyridinemethanol and water is 0.02642 e and 0.03813 e for the most stable 1:1 and 1:2 complexes, respectively. In addition, TD‐B3LYP/6‐311++G∗ ∗ calculations show that formation of water‐OH···N and water‐OH···OH hydrogen bonds makes maximum absorbance wavelength λ max blue‐shifted 8–16 nm and red‐shifted 4–11 nm compared to that of 4‐pyridinemethanol monomer molecule, respectively.