TY - JOUR
T1 - A solid-state density functional theory investigation of the effectof metal substitution (Metal = Mn, Cd, Co) on the terahertz spectra of isomorphous molecular metal 5-(4-pyridyl)tetrazolato complexes
AU - Pellizzeri, Steven
AU - Witko, Ewelina M.
AU - Korter, Timothy M.
AU - Zubieta, Jon
N1 - Funding Information:
This work was supported in part by a grant from the National Science Foundation ( CHE0907787 ). Funding for this work was also provided by a grant from the National Science Foundation CAREER Program ( CHE-0847405 ).
PY - 2013
Y1 - 2013
N2 - The crystal structure and experimental terahertz spectroscopy of an isomorphous series [Mn(C6H4N5)2 (H2O)4]·2H2O (Mn-4PT), [Co(C 6H4N5)2(H2O) 4]·2H2O (Co-4PT), and [Cd(C6H 4N5)2(H2O)4] ·2H2O (Cd-4PT) were compared using solid-state density functional theory (DFT) simulations. The effect of the central metal atom was investigated to determine the influence on the low energy lattice and molecular vibrations exhibited in the region from 10 to 100 cm-1, known as the terahertz (THz) region. Using solid-state DFT the normal modes of these THz vibrations were determined and it was shown that the mass and size of the metal center has a large effect in this region. Each complex exhibited common vibrational modes involving whole ligand motion around the central metal atom. These vibrations were found to shift to lower frequencies with a drastic mass increase; however, this trend is reversed with the smaller mass change between the manganese and cobalt due to the stronger cobalt-nitrogen bond compared to the manganese-nitrogen bond.
AB - The crystal structure and experimental terahertz spectroscopy of an isomorphous series [Mn(C6H4N5)2 (H2O)4]·2H2O (Mn-4PT), [Co(C 6H4N5)2(H2O) 4]·2H2O (Co-4PT), and [Cd(C6H 4N5)2(H2O)4] ·2H2O (Cd-4PT) were compared using solid-state density functional theory (DFT) simulations. The effect of the central metal atom was investigated to determine the influence on the low energy lattice and molecular vibrations exhibited in the region from 10 to 100 cm-1, known as the terahertz (THz) region. Using solid-state DFT the normal modes of these THz vibrations were determined and it was shown that the mass and size of the metal center has a large effect in this region. Each complex exhibited common vibrational modes involving whole ligand motion around the central metal atom. These vibrations were found to shift to lower frequencies with a drastic mass increase; however, this trend is reversed with the smaller mass change between the manganese and cobalt due to the stronger cobalt-nitrogen bond compared to the manganese-nitrogen bond.
KW - 5-(4-Pyridyl)tetrazole
KW - CRYSTAL09
KW - Single crystal X-ray crystallography
KW - Solid-state DFT
KW - Terahertz spectroscopy
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U2 - 10.1016/j.molstruc.2013.05.055
DO - 10.1016/j.molstruc.2013.05.055
M3 - Article
AN - SCOPUS:84879203719
SN - 0022-2860
VL - 1048
SP - 214
EP - 222
JO - Journal of Molecular Structure
JF - Journal of Molecular Structure
ER -