Theoretical Spectroscopy of the N<sub>2</sub>HAr<sup>+</sup> Complex

Brites, V.; Dopfer, Otto; Hochlaf, M.

doi:10.1021/jp806452w

Cited by 5 publications

(4 citation statements)

References 28 publications

(91 reference statements)

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“…Including zero‐point vibrational energy correction, the MP2/aug‐ cc ‐pVDZ(‐PP) dissociation energy ( D 0 ) of this cation is computed ∼0.7 eV, which corresponds to the SnMe

_{4}^{+}

→ CH 3 + SnMe

_{3}^{+}

dissociation. A dissociation energy in the range 0.2–1 eV is characteristic for charge transfer complexes, as established theoretically and experimentally for several tetra‐atomic charge transfer cations45, 46.…”

Section: Resultsmentioning

confidence: 54%

DFT and Ab Initio calculations of spectroscopic properties of tetramethyltin and of its cation

Dhouib

Abderrabba

Essalah

et al. 2011

Int J of Quantum Chemistry

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DFT and ab initio calculations are performed on tetramethyltin (SnMe 4 , TMSn) and its cation. A set of spectroscopic constants for both species are derived. They include equilibrium geometries, rotational constants and vibrational wavenumbers. All quantities are in close agreement with the available experimental data. For the cation, our calculations confirm the C 3v charge transfer structure proposed earlier through the analysis of electron paramagnetic resonance (EPR) experimental data. Using multi reference configuration interaction and time dependant density functional theory (TD-DFT) methodologies, the vertical electronic excitation energies of TMSn and TMSn þ are determined. For the singlet-singlet neutral molecule, our calculated transition energies are distinctly lower than those previously computed. For the TMSn (X 1 A 1 ! 1 1 T 2 ) absorption transition, our computed excitation energy coincides, however, with the experimental value. Predictive data are also given for the TMSn triplets. At the best level of theory, the vertical and the adiabatic ionization energies of TMSn are computed 9.86 eV and 8.74 eV, respectively.

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“…Including zero‐point vibrational energy correction, the MP2/aug‐ cc ‐pVDZ(‐PP) dissociation energy ( D 0 ) of this cation is computed ∼0.7 eV, which corresponds to the SnMe

_{4}^{+}

→ CH 3 + SnMe

_{3}^{+}

Section: Resultsmentioning

confidence: 54%

DFT and Ab Initio calculations of spectroscopic properties of tetramethyltin and of its cation

Dhouib

Abderrabba

Essalah

et al. 2011

Int J of Quantum Chemistry

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“…5 This is characteristic for charge transfer molecular complexes. 9,10,42 In this expansion, we restricted the exponents to i r 4 and j r 4, whereas we needed to expand over k, l and m for higher orders because of the floppiness of the PESs along these coordinates. Therefore, k is needed to be r6 and l r 12 and m r 8.…”

Section: A Analytical Formsmentioning

confidence: 99%

“…The behavior along the R 3 coordinate is common for charge transfer complexes along the lowest dissociation channel. 9,10,37,42 All parts of the PESs related to the bending or torsion are very flat. At fixed equilibrium geometry for all coordinates except one, the barrier to linearity of the OOMg (y 1 ) group was calculated to be B1850 cm À1 and B1800 cm À1 for the 2 A 0 and 2 A 00 components, respectively.…”

Section: B Characteristics Of the 6d Pess And Spectroscopic Implicationsmentioning

confidence: 99%

Generation of full dimensional potential energy surfaces for atmospherically important charge transfer tetratomic complexes: the case of the OMgOO+ radical cation

Yazidi¹,

Hochlaf²

2013

Phys. Chem. Chem. Phys.

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The weakly bound charge transfer OMgOO(+)((2)Π) ion is a quasi-linear-bent Renner-Teller system with a non-zero spin-orbit contribution. The six-dimensional potential energy surfaces (6D-PESs) for the two Renner-Teller components have been generated in internal coordinates. After benchmarking calculations, we show that the newly implemented explicitly correlated coupled cluster approach (RCCSD(T)-F12) in connection with the cc-pVTZ-F12 basis set provides an accurate description of the full 6D-PESs of this molecular system. Both components are bent with low barriers to linearity along the in-plane angles. The potentials are also very flat along the out-of-plane torsional mode. Hence, this confers a pronounced quasi linear character to OMgOO(+). Moreover, the parts of the potentials relative to the middle bond are shallow and strongly coupled to the bending motions. The parts of the PESs corresponding to the OO and MgO external diatom stretch coordinates differ strongly from those relative to the four other internal coordinates. Special care was taken to correctly account for such behaviors during the generation of the grid and fitting procedures. The present theoretical methodology can be used for mapping the 6D-PESs of other atmospherically important charge transfer complexes presenting similar features such as ONNO(+), O4(+), OOCO(+) or M-CO2(+) (where M is an alkali, magnesium or aluminum metal).

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“…This was already observed for other molecular systems, such as N 2 CO + , N 4 + , N 2 HAr + , and HNNH + . 62,[67][68][69]…”

Section: A Description Of the 6d-pessmentioning

confidence: 99%

Explicitly correlated treatment of H2NSi and H2SiN radicals: Electronic structure calculations and rovibrational spectra

Lauvergnat

Senent

Jutier

et al. 2011

The Journal of Chemical Physics

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Various ab initio methods are used to compute the six dimensional potential energy surfaces (6D-PESs) of the ground states of the H(2)NSi and H(2)SiN radicals. They include standard coupled cluster (RCCSD(T)) techniques and the newly developed explicitly correlated RCCSD(T)-F12 methods. For H(2)NSi, the explicitly correlated techniques are viewed to provide data as accurate as the standard coupled cluster techniques, whereas small differences are noticed for H(2)SiN. These PESs are found to be very flat along the out-of-plane and some in-plane bending coordinates. Then, the analytic representations of these PESs are used to solve the nuclear motions by standard perturbation theory and variational calculations. For both isomers, a set of accurate spectroscopic parameters and the vibrational spectrum up to 4000 cm(-1) are predicted. In particular, the analysis of our results shows the occurrence of anharmonic resonances for H(2)SiN even at low energies.

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Theoretical Spectroscopy of the N₂HAr⁺ Complex

Cited by 5 publications

References 28 publications

DFT and Ab Initio calculations of spectroscopic properties of tetramethyltin and of its cation

DFT and Ab Initio calculations of spectroscopic properties of tetramethyltin and of its cation

Generation of full dimensional potential energy surfaces for atmospherically important charge transfer tetratomic complexes: the case of the OMgOO+ radical cation

Explicitly correlated treatment of H2NSi and H2SiN radicals: Electronic structure calculations and rovibrational spectra

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Theoretical Spectroscopy of the N2HAr+ Complex

Cited by 5 publications

References 28 publications

DFT and Ab Initio calculations of spectroscopic properties of tetramethyltin and of its cation

DFT and Ab Initio calculations of spectroscopic properties of tetramethyltin and of its cation

Generation of full dimensional potential energy surfaces for atmospherically important charge transfer tetratomic complexes: the case of the OMgOO+ radical cation

Explicitly correlated treatment of H2NSi and H2SiN radicals: Electronic structure calculations and rovibrational spectra

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Theoretical Spectroscopy of the N₂HAr⁺ Complex