Zero energy kinetic electron and mass analyzed threshold ionization spectroscopy of Na⋅(NH3)n (n=1, 2, and 4) complexes

Peng, Xianzhao; Kong, Wei

doi:10.1063/1.1516796

Cited by 15 publications

(10 citation statements)

References 58 publications

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“…Those calculated at the CCSD͑T͒/aVTZ level are presented in the Supporting Material. 46,47 Nevertheless, our calculated harmonic frequency at the CCSD͑T͒/ awCVTZ level for Na + -NH 3 agrees with the experimental values. [46][47][48][49][50][51][52] These values were obtained by least-squares fits of the experimental band positions in the stretching progressions to the formula T͑ s ͒ − T e = e ͑ s +1/ 2͒ − e x e ͑ s +1/ 2͒ 2 , where e is the harmonic frequency and e x e is the anharmonicity constant.…”

Section: Harmonic Frequencies and Franck-condon Simulationssupporting

confidence: 86%

“…47 They found reasonable agreement between their calculated intensity distributions and their experimental spectrum. 47 They found reasonable agreement between their calculated intensity distributions and their experimental spectrum.…”

Section: Harmonic Frequencies and Franck-condon Simulationsmentioning

confidence: 65%

“…46,47 A possible cause of the discrepancy for the other metals is the anharmonic effect in the neutral M-N stretching mode. Our calculated harmonic frequencies for the M-N stretch are 13-24 cm −1 higher than the experimental fundamentals for M = Al, Ga, In, and Ag but for M = Na, our calculated harmonic frequency falls between the experimental values just as for the cation.…”

Section: Harmonic Frequencies and Franck-condon Simulationsmentioning

confidence: 99%

“…39,40 A major issue in the application of DFT is the choice of the exchange-correlation functional and its systematic improvement. [46][47][48][49][50][51][52] We have calculated the ground state geometries and harmonic frequencies with the DFT and CCSD͑T͒ methods. Current computational benchmarks are usually done for stable molecules and are often compared to experimental data which in itself may not be highly accurate.…”

Section: Introductionmentioning

confidence: 99%

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Benchmark calculations on the adiabatic ionization potentials of M–NH3 (M=Na,Al,Ga,In,Cu,Ag)

Peterson

Dixon

2008

The Journal of Chemical Physics

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The ground states of the M-NH(3) (M=Na,Al,Ga,In,Cu,Ag) complexes and their cations have been studied with density functional theory and coupled cluster [CCSD(T)] methods. The adiabatic ionization potentials (AIPs) of these complexes are calculated, and these are compared to results from high-resolution zero-electron kinetic energy photoelectron spectroscopy. By extrapolating the CCSD(T) energies to the complete basis set (CBS) limit and including the core-valence, scalar relativistic, spin-orbit, and zero-point corrections, the CCSD(T) method is shown to be able to predict the AIPs of these complexes to better than 6 meV or 0.15 kcal/mol. 27 exchange-correlation functionals, including one in the local density approximation, 13 in the generalized gradient approximation (GGA), and 13 with hybrid GGAs, were benchmarked in the calculations of the AIPs. The B1B95, mPW1PW91, B98, B97-1, PBE1PBE, O3LYP, TPSSh, and HCTH93 functionals give an average error of 0.1 eV for all the complexes studied, with the B98 functional alone yielding a maximum error of 0.1 eV. In addition, the calculated metal-ammonia harmonic stretching frequencies with the CCSD(T) method are in excellent agreement with their experimental values, whereas the B3LYP method tends to underestimate these stretching frequencies. The metal-ammonia binding energies were also calculated at the CCSD(T)/CBS level, and are in excellent agreement with the available experimental values considering the error limits, except for Ag-NH(3) and Ag(+)-NH(3), where the calculations predict stronger bond energies than measured by about 4 kcal/mol, just outside the experimental error bars of +/-3 kcal/mol.

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Section: Harmonic Frequencies and Franck-condon Simulationssupporting

confidence: 86%

Section: Harmonic Frequencies and Franck-condon Simulationsmentioning

confidence: 65%

Section: Harmonic Frequencies and Franck-condon Simulationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Benchmark calculations on the adiabatic ionization potentials of M–NH3 (M=Na,Al,Ga,In,Cu,Ag)

Peterson

Dixon

2008

The Journal of Chemical Physics

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“…Consequently, only a few vibronic spectra have so far been reported for metal complexes with two or more neutral polyatomic molecular ligands. 1,14,15 In the present work, we report the single-photon ionization and pulsed-field ionization zero electron kinetic energy ͑ZEKE͒ photoelectron spectroscopy of Cu͑NH 3 ͒ 2 and Cu͑ND 3 ͒ 2 . The vibrationally resolved ZEKE spectra, coupled with ab initio calculations, show that the neutral and ionic ground electronic states of Cu͑NH 3 ͒ 2 prefer a linear N-Cu-N configuration.…”

Section: Introductionmentioning

confidence: 98%

Pulsed-field ionization electron spectroscopy and conformation of copper-diammonia

Sohnlein

Yang

et al. 2005

The Journal of Chemical Physics

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Copper-diammonia, Cu(NH3)2, and its deuterated species, Cu(ND3)2, are produced in supersonic molecular beams and studied by pulsed-field ionization zero electron kinetic energy photoelectron spectroscopy and ab initio calculations. Structural isomers with a copper atom binding to an ammonia dimer or two ammonia molecules are obtained by the calculations. By comparing the experimental measurements to the theoretical calculations, the neutral and ionic forms of copper-diammonia are determined to be in a doubly bound linear conformation in their ground electronic states. The adiabatic ionization potentials of Cu(NH3)2 and Cu(ND3)2 are measured as 29,532 (5) and 29,313 (5) cm(-1), respectively. The metal-ligand symmetric stretching frequencies are measured to be 436 cm(-1) for Cu+-(NH3)2 and 398 cm(-1) for Cu+-(ND3)2, and the metal-ligand bending frequencies 75,139 cm(-1) for CuCu+-(NH3)2 and 70125 cm(-1) for CuCu+-(ND3)2. Moreover, the dissociation energy of Cu(NH3)2-->CuNH3+NH3 is determined to be 11(3) kcal mol(-1) through a thermodynamic relationship.

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Gas Phase Ion Chemistry

Gross

2004

Mass Spectrometry

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Zero energy kinetic electron and mass analyzed threshold ionization spectroscopy of Na⋅(NH3)n (n=1, 2, and 4) complexes

Cited by 15 publications

References 58 publications

Benchmark calculations on the adiabatic ionization potentials of M–NH3 (M=Na,Al,Ga,In,Cu,Ag)

Benchmark calculations on the adiabatic ionization potentials of M–NH3 (M=Na,Al,Ga,In,Cu,Ag)

Pulsed-field ionization electron spectroscopy and conformation of copper-diammonia

Gas Phase Ion Chemistry

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