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

Steven Pellizzeri, Ewelina M. Witko, Timothy Michael Korter, Jon A Zubieta

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

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.

Original languageEnglish (US)
Pages (from-to)214-222
Number of pages9
JournalJournal of Molecular Structure
Volume1048
DOIs
StatePublished - 2013

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Density functional theory
Substitution reactions
Metals
Manganese
Cobalt
Nitrogen
Terahertz spectroscopy
Molecular vibrations
Atoms
Lattice vibrations
Crystal structure
Ligands

Keywords

  • 5-(4-Pyridyl)tetrazole
  • CRYSTAL09
  • Single crystal X-ray crystallography
  • Solid-state DFT
  • Terahertz spectroscopy

ASJC Scopus subject areas

  • Spectroscopy
  • Analytical Chemistry
  • Inorganic Chemistry
  • Organic Chemistry

Cite this

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title = "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",
abstract = "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.",
keywords = "5-(4-Pyridyl)tetrazole, CRYSTAL09, Single crystal X-ray crystallography, Solid-state DFT, Terahertz spectroscopy",
author = "Steven Pellizzeri and Witko, {Ewelina M.} and Korter, {Timothy Michael} and Zubieta, {Jon A}",
year = "2013",
doi = "10.1016/j.molstruc.2013.05.055",
language = "English (US)",
volume = "1048",
pages = "214--222",
journal = "Journal of Molecular Structure",
issn = "0022-2860",
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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 Michael

AU - Zubieta, Jon A

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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