The molecular and electronic states of 1,2,4,5-tetrazine studied by VUV absorption, near-threshold electron energy-loss spectroscopy and ab initio multi-reference configuration interaction studies

Michael H. Palmer, Hamish McNab, David Reed, Anne Pollacchi, Isobel C. Walker, Martyn F. Guest, M. R F Siggel

Research output: Contribution to journalArticle

Abstract

The VUV electronic absorption spectrum of 1,2,4,5-tetrazine has been re-investigated, and together with electron energy-loss spectra has led to identification of a number of new excited states. The valence and Rydberg excited states have been studied by multi-reference multi-root configuration interaction studies using MRDCI techniques. Initial studies with the RPA and TDA methods gave almost identical results for the excitation energies, but there is a substantial energy-lowering in the MRDCI calculations, which improves agreement with experiment substantially; these differences are a result of the double, triple and quadruple excited reference configurations included in the reference set of the latter method. The 1pp* excitations are calculated rather higher than experiment, except for the lowest-lying (weak) 1B2u state at 5.0 eV. The calculated order for the next three pp* states is 1B1u (weak) followed by 1B2u (strong) and 1B1u (strong), the last two bands being responsible for the dominant absorption near 7.5 and 8.5 eV. All of this group of four bands involve excitations from the pair of MOs 1b2g and 1b1g into the 1a*u and 4b*3u VMOs. The sequence of np* states are in a similar order to the pp* excitations, with respect to the upper state, and the two lowest singlet states, 1B3u and 1Au are reasonably well determined. The triplet states follow a similar order to the singlets, and again the dominance of the effect of the two lowest VMOs is demonstrated, but considerable differences between the weighting of leading configurations occurs between singlet and triplet manifolds. The non-diagonal TDA method has been used to reconsider the UV-photoelectron spectrum. The ionisation potentials for tetrazine are reinterpreted with the first three bands being regrouped into 1, 2, 2 ionisations respectively. The ground state properties of tetrazine suggest that the NQR spectrum will show a principal axis 14N quadrupole coupling constant larger than the other known azines. The decline in diamagnetic susceptibility anisotropy in tetrazine, relative to benzene and pyridine, is indicative of lower resonance energy.

Original languageEnglish
Pages (from-to)191-211
Number of pages21
JournalChemical Physics
Volume214
Issue number2-3
Publication statusPublished - 15 Jan 1997

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configuration interaction
energy dissipation
electron energy
thresholds
electronics
spectroscopy
excitation
azines
configurations
electronic spectra
ionization potentials
atomic energy levels
energy
pyridines
photoelectrons
quadrupoles
benzene
valence
absorption spectra
magnetic permeability

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Palmer, Michael H. ; McNab, Hamish ; Reed, David ; Pollacchi, Anne ; Walker, Isobel C. ; Guest, Martyn F. ; Siggel, M. R F. / The molecular and electronic states of 1,2,4,5-tetrazine studied by VUV absorption, near-threshold electron energy-loss spectroscopy and ab initio multi-reference configuration interaction studies. In: Chemical Physics. 1997 ; Vol. 214, No. 2-3. pp. 191-211.
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abstract = "The VUV electronic absorption spectrum of 1,2,4,5-tetrazine has been re-investigated, and together with electron energy-loss spectra has led to identification of a number of new excited states. The valence and Rydberg excited states have been studied by multi-reference multi-root configuration interaction studies using MRDCI techniques. Initial studies with the RPA and TDA methods gave almost identical results for the excitation energies, but there is a substantial energy-lowering in the MRDCI calculations, which improves agreement with experiment substantially; these differences are a result of the double, triple and quadruple excited reference configurations included in the reference set of the latter method. The 1pp* excitations are calculated rather higher than experiment, except for the lowest-lying (weak) 1B2u state at 5.0 eV. The calculated order for the next three pp* states is 1B1u (weak) followed by 1B2u (strong) and 1B1u (strong), the last two bands being responsible for the dominant absorption near 7.5 and 8.5 eV. All of this group of four bands involve excitations from the pair of MOs 1b2g and 1b1g into the 1a*u and 4b*3u VMOs. The sequence of np* states are in a similar order to the pp* excitations, with respect to the upper state, and the two lowest singlet states, 1B3u and 1Au are reasonably well determined. The triplet states follow a similar order to the singlets, and again the dominance of the effect of the two lowest VMOs is demonstrated, but considerable differences between the weighting of leading configurations occurs between singlet and triplet manifolds. The non-diagonal TDA method has been used to reconsider the UV-photoelectron spectrum. The ionisation potentials for tetrazine are reinterpreted with the first three bands being regrouped into 1, 2, 2 ionisations respectively. The ground state properties of tetrazine suggest that the NQR spectrum will show a principal axis 14N quadrupole coupling constant larger than the other known azines. The decline in diamagnetic susceptibility anisotropy in tetrazine, relative to benzene and pyridine, is indicative of lower resonance energy.",
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The molecular and electronic states of 1,2,4,5-tetrazine studied by VUV absorption, near-threshold electron energy-loss spectroscopy and ab initio multi-reference configuration interaction studies. / Palmer, Michael H.; McNab, Hamish; Reed, David; Pollacchi, Anne; Walker, Isobel C.; Guest, Martyn F.; Siggel, M. R F.

In: Chemical Physics, Vol. 214, No. 2-3, 15.01.1997, p. 191-211.

Research output: Contribution to journalArticle

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T1 - The molecular and electronic states of 1,2,4,5-tetrazine studied by VUV absorption, near-threshold electron energy-loss spectroscopy and ab initio multi-reference configuration interaction studies

AU - Palmer, Michael H.

AU - McNab, Hamish

AU - Reed, David

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AU - Guest, Martyn F.

AU - Siggel, M. R F

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AB - The VUV electronic absorption spectrum of 1,2,4,5-tetrazine has been re-investigated, and together with electron energy-loss spectra has led to identification of a number of new excited states. The valence and Rydberg excited states have been studied by multi-reference multi-root configuration interaction studies using MRDCI techniques. Initial studies with the RPA and TDA methods gave almost identical results for the excitation energies, but there is a substantial energy-lowering in the MRDCI calculations, which improves agreement with experiment substantially; these differences are a result of the double, triple and quadruple excited reference configurations included in the reference set of the latter method. The 1pp* excitations are calculated rather higher than experiment, except for the lowest-lying (weak) 1B2u state at 5.0 eV. The calculated order for the next three pp* states is 1B1u (weak) followed by 1B2u (strong) and 1B1u (strong), the last two bands being responsible for the dominant absorption near 7.5 and 8.5 eV. All of this group of four bands involve excitations from the pair of MOs 1b2g and 1b1g into the 1a*u and 4b*3u VMOs. The sequence of np* states are in a similar order to the pp* excitations, with respect to the upper state, and the two lowest singlet states, 1B3u and 1Au are reasonably well determined. The triplet states follow a similar order to the singlets, and again the dominance of the effect of the two lowest VMOs is demonstrated, but considerable differences between the weighting of leading configurations occurs between singlet and triplet manifolds. The non-diagonal TDA method has been used to reconsider the UV-photoelectron spectrum. The ionisation potentials for tetrazine are reinterpreted with the first three bands being regrouped into 1, 2, 2 ionisations respectively. The ground state properties of tetrazine suggest that the NQR spectrum will show a principal axis 14N quadrupole coupling constant larger than the other known azines. The decline in diamagnetic susceptibility anisotropy in tetrazine, relative to benzene and pyridine, is indicative of lower resonance energy.

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