**Ab initio calculations of the structures and vibrational spectra of ethene complexes.** / Alexander, Bruce D.; Dines, Trevor J.

Research output: Contribution to journal › Article

Alexander, BD & Dines, TJ 2004, 'Ab initio calculations of the structures and vibrational spectra of ethene complexes' *Journal of Physical Chemistry A*, vol 108, no. 1, pp. 146-156. DOI: 10.1021/jp0357020

Alexander, B. D., & Dines, T. J. (2004). *Ab initio calculations of the structures and vibrational spectra of ethene complexes*. *Journal of Physical Chemistry A*, *108*(1), 146-156. DOI: 10.1021/jp0357020

Alexander BD, Dines TJ. Ab initio calculations of the structures and vibrational spectra of ethene complexes. Journal of Physical Chemistry A. 2004 Jan;108(1):146-156. Available from, DOI: 10.1021/jp0357020

@article{86d1fef8f6ea4ce586a4b85a429d8bcb,

title = "Ab initio calculations of the structures and vibrational spectra of ethene complexes",

keywords = "Effective core potentials, Transition-metal atoms, Generalized gradient approximation, Density-functional thermochemistry, Normal-coordinate analysis, Molecular calculations, Platinum(0) complexes, Correlation energy, Exact exchange, Ethylene",

author = "Alexander, {Bruce D.} and Dines, {Trevor J.}",

note = "dc.publisher: American Chemical Society",

year = "2004",

month = "1",

doi = "10.1021/jp0357020",

volume = "108",

pages = "146--156",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Ab initio calculations of the structures and vibrational spectra of ethene complexes

AU - Alexander,Bruce D.

AU - Dines,Trevor J.

N1 - dc.publisher: American Chemical Society

PY - 2004/1

Y1 - 2004/1

N2 - To facilitate an objective comparison of the efficacy of the simulation of structural parameters and vibrational spectra of transition-metal complexes of commonly used ab initio methods, the geometries of the ethene complexes of Ni(0) and Ni(H) have been optimized using both ab initio and density functional theory (DFT) calculations and a wide variety of basis sets. The harmonic vibrational spectra of [Ni(C2H4)] and [Ni(C2H4)](2+) have been evaluated from the optimized geometries at Hartree-Fock, post-Hartree-Fock Moller-Plesset perturbation theory, MP2, and a range of DFT functionals. Upon comparison with experimental data, it has been found that hybrid DFT functionals, specifically B3-LYP, afford the most accurate fit to the experimental data. This is especially the case when using the all-electron DZVP basis set, which provides highly accurate results. The use of the effective core potential LanL2DZ basis set has been found to achieve a comparable level of accuracy to the DZVP basis set, at a fraction of the computational efficiency. Extension of these calculations to ethene complexes of other transition metals has revealed trends in their structures and vibrational spectra.

AB - To facilitate an objective comparison of the efficacy of the simulation of structural parameters and vibrational spectra of transition-metal complexes of commonly used ab initio methods, the geometries of the ethene complexes of Ni(0) and Ni(H) have been optimized using both ab initio and density functional theory (DFT) calculations and a wide variety of basis sets. The harmonic vibrational spectra of [Ni(C2H4)] and [Ni(C2H4)](2+) have been evaluated from the optimized geometries at Hartree-Fock, post-Hartree-Fock Moller-Plesset perturbation theory, MP2, and a range of DFT functionals. Upon comparison with experimental data, it has been found that hybrid DFT functionals, specifically B3-LYP, afford the most accurate fit to the experimental data. This is especially the case when using the all-electron DZVP basis set, which provides highly accurate results. The use of the effective core potential LanL2DZ basis set has been found to achieve a comparable level of accuracy to the DZVP basis set, at a fraction of the computational efficiency. Extension of these calculations to ethene complexes of other transition metals has revealed trends in their structures and vibrational spectra.

KW - Effective core potentials

KW - Transition-metal atoms

KW - Generalized gradient approximation

KW - Density-functional thermochemistry

KW - Normal-coordinate analysis

KW - Molecular calculations

KW - Platinum(0) complexes

KW - Correlation energy

KW - Exact exchange

KW - Ethylene

U2 - 10.1021/jp0357020

DO - 10.1021/jp0357020

M3 - Article

VL - 108

SP - 146

EP - 156

JO - Journal of Physical Chemistry A

T2 - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 1

ER -