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Hybrid DFT study of the hyperfine coupling constants of methyl radicals in model matrix lattices
Author(s) -
Takada Tomoya,
Tachikawa Hiroto
Publication year - 2005
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20646
Subject(s) - chemistry , radical , density functional theory , hyperfine structure , ab initio , computational chemistry , hydrogen atom , hyperfine coupling , matrix (chemical analysis) , lattice (music) , coupling constant , hydrogen , quantum mechanics , physics , group (periodic table) , organic chemistry , chromatography , acoustics
The hyperfine coupling constants of hydrogen atom (H‐hfcc's, a H ) of methyl radical (CH 3 ) in matrices have been calculated by means of the hybrid density functional theory (DFT) and ab initio methods in order to elucidate the effect of matrices on the H‐hfcc of CH 3 . Three typical matrices (X = CH 4 , H 2 , and Ar) were examined in the calculations. The systems calculated in the present work, denoted by CH 3 (X) n , are CH 3 (H 2 ) n ( n = 12 and 20), CH 3 (Ar) n ( n = 12 and 18), and CH 3 (CH 4 ) n ( n = 12 and 18). The Møller–Plesset type 2 (MP2) and B3LYP methods were applied to the H‐hfcc calculation. The H‐hfcc of methyl radical was slightly perturbed by the interaction with matrices lattice, and it was shifted from that of free methyl radical ( a H = −23.03 G). The mechanism of the shift of H‐hfcc of CH 3 in matrices lattice was discussed on the basis of theoretical results. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005