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Geometry optimization of organometallic complexes: A study of basis sets
Author(s) -
Williamson Rodney L.,
Hall Michael B.
Publication year - 1987
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.560320749
Subject(s) - cyclopentadienyl complex , bond length , metal , chemistry , basis set , basis (linear algebra) , benzene , bond strength , crystallography , group 2 organometallic chemistry , molecular geometry , computational chemistry , geometry , molecule , mathematics , density functional theory , organic chemistry , crystal structure , catalysis , adhesive , layer (electronics)
Total geometry optimizations are reported for Cr(CO) 6 , HMn(CO) 5 , Fe(CO) 5 , Ni(CO) 4 , Cr(C 6 H 6 ) 2 , Fe(C 5 H 5 ) 2 , Ni(C 4 H 4 ) 2 , Cr(NO) 4 , (C 5 H 5 )Mn(CO) 3 , and (C 6 H 6 )Cr(CO) 3 . A variety of basis sets were examined, and, based on the results, a relatively compact and accurate basis set is proposed. The differences between the calculated and experimental metal‐carbonyl, metal‐benzene, and metal‐nitrosyl bond distances average 0.03, 0.08, and 0.07 Å, respectively. Calculated metal‐cyclopentadienyl bond lengths were found to be an average of 0.15 Å longer than experimental bond lengths. Addition of electron correlation at the perfect pairing GVB level reduced the average difference in the metal‐cyclopentadienyl bond length to 0.08 Å.