Ab initio calculation of the electronic spectrum and ionization potentials of hydrazine

Habas, Marie-Pierre; Baraille, Isabelle; Larrieu, C.; Chaillet, M.

doi:10.1016/s0301-0104(97)00083-9

Cited by 13 publications

(13 citation statements)

References 34 publications

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“…1. The C 2 symmetry of hydrazine in the S 0 state is consistent with the results of previous studies with ab initio calculations [30][31][32][33][34][35][36] and experiments, [37][38][39][40][41][42][43][44][45] and is similar to that of the hydrazino group of phenylhydrazine in the S 0 state. The planar structure of hydrazine in the S 1 state is also similar to that of the hydrazino group of phenylhydrazine in the S 1 state, though one of the H b atoms is slightly bent out of the ring plane in phenyhydrazine.…”

Section: Resultssupporting

confidence: 91%

Theoretical and REMPI spectroscopic study on phenylhydrazine and phenylhydrazine–(Ar)n (n = 1, 2) van der Waals complexes

Xiao

et al. 2009

Phys. Chem. Chem. Phys.

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Phenylhydrazine and its van der Waals complexes with one or two argon atoms were investigated with theoretical calculations and resonant two photon ionization (R2PI) spectroscopy. The ab initio and DFT calculations found a conversion of the orbital hybridization of the Nbeta atom from sp3-like in the S0 state to sp2-like in the S1 state, suggesting that the lone pair electrons of the Nbeta atom are involved in a super p-p-pi conjugation over the skeleton of phenylhydrazine in the S1 state. The structural change of the hydrazino group in the S1<--S0 electronic transition was reflected by the vibrational excitations of the hydrazino group observed in the 1C-R2PI spectrum. The band origin of the S1<--S0 transition is determined to be 33610 cm(-1) and the adiabatic ionization energy (IE) of phenylhydrazine, measured by 2C-R2PI spectroscopy, is 62829+/-15 cm(-1). The S1<--S0 electronic transitions of phenylhydrazine-Ar and phenylhydrazine-Ar2 complexes were also observed in the 1C-R2PI spectrum, and their band origins are, respectively, red-shifted by 39 and 80 cm(-1) from that of phenylhydrazine.

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Section: Resultssupporting

confidence: 91%

Theoretical and REMPI spectroscopic study on phenylhydrazine and phenylhydrazine–(Ar)n (n = 1, 2) van der Waals complexes

Xiao

et al. 2009

Phys. Chem. Chem. Phys.

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“…22 Past studies on the ionic species have been devoted to the N 2 H 4 + cation and its various structures. 18,23 As far as the negative ions are considered, an experimental study of the dissociative electron attachment to hydrazine was performed and formation of NH 2 -by the attachment of an electron to H 2 NNH 2 was reported. 24 To the best of our knowledge, the possibility of formation of stable N 2 H 4 -anions has, to date, been investigated neither experimentally nor theoretically, even though the significant SCF dipole moment of 5.5 D for I 22 leaves no doubt 25 that a dipole-bound anion of this isomer may be formed.…”

Section: Hydrazine and Its Tautomermentioning

confidence: 99%

“…The parent compound, hydrazine (H 2 NNH 2 ), is kinetically stable, but thermodynamically unstable . It is one of the simplest nitrogen compounds and an important rocket fuel; thus it has been well characterized experimentally − and theoretically. − …”

Section: Introductionmentioning

confidence: 99%

“…1 It is one of the simplest nitrogen compounds and an important rocket fuel; thus it has been well characterized experimentally 2-10 and theoretically. [11][12][13][14][15][16][17][18][19][20] The C 2 symmetry gauche conformer of hydrazine (see Figure 1, III) is known experimentally and theoretically to be the most stable structure. Rotation around the N-N bond leads to the less stable staggered (anti) C 2h conformer and an eclipsed (syn) structure.…”

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confidence: 99%

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Dipole-Bound Anion of the HNNH₃ Isomer of Hydrazine. An Ab Initio Study

1999

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The possibility of electron binding to the HNNH 3 and H 2 NNH 2 tautomers of hydrazine was studied at the coupled cluster level of theory with single, double, and noniterative triple excitations. The HNNH 3 tautomer, with a dipole moment of 5.4 D, binds an electron by 1076 cm -1 whereas the H 2 NNH 2 tautomer forms neither a dipole-nor valence-bound anionic state. It is suggested that the HNNH 3 tautomer, which is kinetically stable but thermodynamically unstable relative to H 2 NNH 2 , may be formed by photodetachment from the N 2 H 4 -species examined in this work.

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“…[1][2][3][4][5][6][7][8][9][10] Due to its structural simplicity, hydrazine has been extensively studied as a model compound. [2][3][4][5][6][7][8] Despite the apparent absence of complicating factors, such as substituents, the origin of the barrier to its internal rotation about the N-N bond seems not to be either simple or fully resolved.…”

Section: Introductionmentioning

confidence: 99%

Origin of Rotational Barriers of the N−N Bond in Hydrazine: NBO Analysis

et al. 2006

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Hydrazine passes through two transition states, TS1 (phi = 0 degrees ) and TS2 (phi = 180 degrees ), in the course of internal rotation around its N-N bond. The origin of the corresponding rotational barriers in hydrazine has been extensively studied by experimental and theoretical methods. Here, we used natural bond orbital (NBO) analysis and energy decomposition of rotational barrier energy (DeltaE(barrier)) to understand the origin of the torsional potential energy profile of this molecule. DeltaE(barrier) was dissected into structural (DeltaE(struc)), steric exchange (DeltaE(steric)), and hyperconjugative (DeltaE(deloc)) energy contributions. In both transition states, the major barrier-forming contribution is DeltaE(deloc). The TS2 barrier is lowered by pyramidalization of nitrogen atoms through lowering DeltaE(struc), not by N-N bond lengthening through lowering DeltaE(steric). Higher pyramidality of nitrogen atoms of TS2 than that of TS1 explains well why the N-N bond of TS2 is longer than that of TS1. Finally, the steric repulsion between nitrogen lone pairs does not determine the rotational barrier; nuclear-nuclear Coulombic repulsion between outer H/H atoms in TS1 plays an important role in increasing DeltaE(struc). Taken together, we explain the reason for the different TS1 and TS2 barriers. We show that NBO analysis is a useful tool for understanding structures and potential energy surfaces of compounds containing the N-N bond.

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Ab initio calculation of the electronic spectrum and ionization potentials of hydrazine

Cited by 13 publications

References 34 publications

Theoretical and REMPI spectroscopic study on phenylhydrazine and phenylhydrazine–(Ar)n (n = 1, 2) van der Waals complexes

Theoretical and REMPI spectroscopic study on phenylhydrazine and phenylhydrazine–(Ar)n (n = 1, 2) van der Waals complexes

Dipole-Bound Anion of the HNNH₃ Isomer of Hydrazine. An Ab Initio Study

Origin of Rotational Barriers of the N−N Bond in Hydrazine: NBO Analysis

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Ab initio calculation of the electronic spectrum and ionization potentials of hydrazine

Cited by 13 publications

References 34 publications

Theoretical and REMPI spectroscopic study on phenylhydrazine and phenylhydrazine–(Ar)n (n = 1, 2) van der Waals complexes

Theoretical and REMPI spectroscopic study on phenylhydrazine and phenylhydrazine–(Ar)n (n = 1, 2) van der Waals complexes

Dipole-Bound Anion of the HNNH3 Isomer of Hydrazine. An Ab Initio Study

Origin of Rotational Barriers of the N−N Bond in Hydrazine: NBO Analysis

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Dipole-Bound Anion of the HNNH₃ Isomer of Hydrazine. An Ab Initio Study