Theoretical study of the Cu(H2O) and Cu(NH3) complexes and their photolysis products

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Abstract

Equilibrium geometries, binding energies, harmonic vibrational frequencies, infrared intensities, and isotopic shifts have been calculated for the Cu(H2O) and Cu(NH3) complexes and their photolysis products [HCuOH, CuOH, HCu(NH2), and Cu(NH2)] using Kohn-Sham theory with a gradient-corrected nonlocal potential. Cu(H 2O) and Cu(NH3) are weakly bound systems, their binding energies are estimated to be 3.7 and 12.0 kcal/mol, respectively. The HCuOH and HCu(NH2) insertion products are 2.4 and 6.3 kcal/mol less stable than Cu(H2O) and Cu(NH3), whereas H+CuOH and H+Cu(NH 2) lie 49.7 and 58.0 kcal/mol above Cu(H2O) and Cu(NH 3), respectively. The calculated harmonic frequencies agree remarkably well with matrix-isolation infrared data; the agreement is always within 50 cm-1 (30 cm-1 on average) and the mean relative deviation from the experimental frequencies is 2.8%. The calculated isotopic frequency shifts are in close agreement with experiment, except for normal modes, where two or more types of vibrations are coupled. For these modes, the sum of the isotopic shifts is accurately reproduced. The sensitivity of the calculated properties to the numerical integration grid has been investigated and it is found that the grid usually used for main-group molecules has to be extended to obtain numerically stable vibrational properties for transition metal-ligand systems.

Original languageEnglish
Pages (from-to)1860-1870
Number of pages11
JournalThe Journal of Chemical Physics
Volume103
Issue number5
Publication statusPublished - 1995

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Photolysis
Binding energy
photolysis
Infrared radiation
Vibrational spectra
products
binding energy
grids
Transition metals
harmonics
shift
Ligands
numerical integration
frequency shift
Molecules
Geometry
insertion
isolation
transition metals
deviation

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

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title = "Theoretical study of the Cu(H2O) and Cu(NH3) complexes and their photolysis products",
abstract = "Equilibrium geometries, binding energies, harmonic vibrational frequencies, infrared intensities, and isotopic shifts have been calculated for the Cu(H2O) and Cu(NH3) complexes and their photolysis products [HCuOH, CuOH, HCu(NH2), and Cu(NH2)] using Kohn-Sham theory with a gradient-corrected nonlocal potential. Cu(H 2O) and Cu(NH3) are weakly bound systems, their binding energies are estimated to be 3.7 and 12.0 kcal/mol, respectively. The HCuOH and HCu(NH2) insertion products are 2.4 and 6.3 kcal/mol less stable than Cu(H2O) and Cu(NH3), whereas H+CuOH and H+Cu(NH 2) lie 49.7 and 58.0 kcal/mol above Cu(H2O) and Cu(NH 3), respectively. The calculated harmonic frequencies agree remarkably well with matrix-isolation infrared data; the agreement is always within 50 cm-1 (30 cm-1 on average) and the mean relative deviation from the experimental frequencies is 2.8{\%}. The calculated isotopic frequency shifts are in close agreement with experiment, except for normal modes, where two or more types of vibrations are coupled. For these modes, the sum of the isotopic shifts is accurately reproduced. The sensitivity of the calculated properties to the numerical integration grid has been investigated and it is found that the grid usually used for main-group molecules has to be extended to obtain numerically stable vibrational properties for transition metal-ligand systems.",
author = "Imre P{\'a}pai",
year = "1995",
language = "English",
volume = "103",
pages = "1860--1870",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
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TY - JOUR

T1 - Theoretical study of the Cu(H2O) and Cu(NH3) complexes and their photolysis products

AU - Pápai, Imre

PY - 1995

Y1 - 1995

N2 - Equilibrium geometries, binding energies, harmonic vibrational frequencies, infrared intensities, and isotopic shifts have been calculated for the Cu(H2O) and Cu(NH3) complexes and their photolysis products [HCuOH, CuOH, HCu(NH2), and Cu(NH2)] using Kohn-Sham theory with a gradient-corrected nonlocal potential. Cu(H 2O) and Cu(NH3) are weakly bound systems, their binding energies are estimated to be 3.7 and 12.0 kcal/mol, respectively. The HCuOH and HCu(NH2) insertion products are 2.4 and 6.3 kcal/mol less stable than Cu(H2O) and Cu(NH3), whereas H+CuOH and H+Cu(NH 2) lie 49.7 and 58.0 kcal/mol above Cu(H2O) and Cu(NH 3), respectively. The calculated harmonic frequencies agree remarkably well with matrix-isolation infrared data; the agreement is always within 50 cm-1 (30 cm-1 on average) and the mean relative deviation from the experimental frequencies is 2.8%. The calculated isotopic frequency shifts are in close agreement with experiment, except for normal modes, where two or more types of vibrations are coupled. For these modes, the sum of the isotopic shifts is accurately reproduced. The sensitivity of the calculated properties to the numerical integration grid has been investigated and it is found that the grid usually used for main-group molecules has to be extended to obtain numerically stable vibrational properties for transition metal-ligand systems.

AB - Equilibrium geometries, binding energies, harmonic vibrational frequencies, infrared intensities, and isotopic shifts have been calculated for the Cu(H2O) and Cu(NH3) complexes and their photolysis products [HCuOH, CuOH, HCu(NH2), and Cu(NH2)] using Kohn-Sham theory with a gradient-corrected nonlocal potential. Cu(H 2O) and Cu(NH3) are weakly bound systems, their binding energies are estimated to be 3.7 and 12.0 kcal/mol, respectively. The HCuOH and HCu(NH2) insertion products are 2.4 and 6.3 kcal/mol less stable than Cu(H2O) and Cu(NH3), whereas H+CuOH and H+Cu(NH 2) lie 49.7 and 58.0 kcal/mol above Cu(H2O) and Cu(NH 3), respectively. The calculated harmonic frequencies agree remarkably well with matrix-isolation infrared data; the agreement is always within 50 cm-1 (30 cm-1 on average) and the mean relative deviation from the experimental frequencies is 2.8%. The calculated isotopic frequency shifts are in close agreement with experiment, except for normal modes, where two or more types of vibrations are coupled. For these modes, the sum of the isotopic shifts is accurately reproduced. The sensitivity of the calculated properties to the numerical integration grid has been investigated and it is found that the grid usually used for main-group molecules has to be extended to obtain numerically stable vibrational properties for transition metal-ligand systems.

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