Negative ion photoelectron spectroscopy confirms the prediction that D3h carbon trioxide (CO3) has a singlet ground state

Density functional calculations of neutral and anionic tantalum trimer monoxide are presented. The calculations were performed employing scalar quasi–relativistic effective core potentials. Different isomers of Ta3O and Ta3O- were studied in order to determinethe ground state structures. For both systems a planar C2vstructure with an edge-boundoxygen atom was found as ground state. Equilibrium structure parameters, harmonic frequencies, adiabatic electron affinity and Kohn-Sham orbital diagrams are reported. The calculated values are in good agreement with the available experimental data obtained from negative ion photoelectron spectroscopy. The correlation diagram between the neutral and anionic Ta3O shows that, in agreement with the experimental prediction, the extra electron in the anionic system occupies a nonbonding orbital.

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Negative ion photoelectron spectroscopy of the ground state, dipole-bound dimeric anion, (HF)2−

The Journal of Chemical Physics ◽

10.1063/1.474653 ◽

1997 ◽

Vol 107 (8) ◽

pp. 2962-2967 ◽

Cited By ~ 57

Author(s):

Jay H. Hendricks ◽

Helen L. de Clercq ◽

Svetlana A. Lyapustina ◽

Kit H. Bowen

Keyword(s):

Ground State ◽

Photoelectron Spectroscopy ◽

Negative Ion

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Negative Ion Photoelectron Spectroscopy of NH2-(NH3)1 and NH2-(NH3)2: Gas Phase Basicities of Partially Solvated Anions

The Journal of Physical Chemistry ◽

10.1021/j100024a006 ◽

1995 ◽

Vol 99 (24) ◽

pp. 9675-9680 ◽

Cited By ~ 13

Author(s):

Joseph T. Snodgrass ◽

James V. Coe ◽

Carl B. Freidhoff ◽

Kevin M. McHugh ◽

Susan T. Arnold ◽

...

Keyword(s):

Gas Phase ◽

Photoelectron Spectroscopy ◽

Negative Ion ◽

Gas Phase Basicities

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Photoelectron spectroscopy and photochemistry of tetracyanoethylene radical anion in the gas phase

Chemical Physics Letters ◽

10.1016/j.cplett.2012.08.035 ◽

2012 ◽

Vol 550 ◽

pp. 15-18 ◽

Cited By ~ 13

Author(s):

Dmitry Khuseynov ◽

Matthew T. Fontana ◽

Andrei Sanov

Keyword(s):

Gas Phase ◽

Photoelectron Spectroscopy ◽

Radical Anion

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The Ground State of (CS)4Is Different from That of (CO)4: An Experimental Test of a Computational Prediction by Negative Ion Photoelectron Spectroscopy

The Journal of Physical Chemistry A ◽

10.1021/jp406160d ◽

2013 ◽

Vol 117 (33) ◽

pp. 7841-7846 ◽

Cited By ~ 8

Author(s):

Jian Zhang ◽

David A. Hrovat ◽

Zhenrong Sun ◽

Xiaoguang Bao ◽

Weston Thatcher Borden ◽

...

Keyword(s):

Experimental Test ◽

Ground State ◽

Photoelectron Spectroscopy ◽

Computational Prediction ◽

Negative Ion

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Photoionization dynamics in CS fragmented from CS2 studied by high-resolution photoelectron spectroscopy

Canadian Journal of Chemistry ◽

10.1139/v04-015 ◽

2004 ◽

Vol 82 (6) ◽

pp. 744-749

Author(s):

Anouk M Rijs ◽

Ellen HG Backus ◽

Cornelis A de Lange

Keyword(s):

High Resolution ◽

Triplet State ◽

Key Words ◽

Excited States ◽

Ground State ◽

Photoelectron Spectroscopy ◽

Electronic States ◽

Reactive Intermediates ◽

Photoelectron Spectra ◽

Singlet Ground State

The photoionization dynamics of CS have been studied using high-resolution laser photoelectron spectroscopy. The photodissociation of CS2 at ~308 nm results in highly rotationally excited CS in its X1Σ+ singlet ground state, as well as in rotationally cold CS in the excited a3Π triplet state. The ground-state CS fragments are formed together with sulfur in its 3P, 1D, and 1S electronic states; triplet CS is produced in coincidence with ground-state sulfur (3P). In both channels the photoelectron spectra are dominated by Δv = 0 propensity, but transitions involving Δv = 1 and 2 are also observed. Key words: photoelectron spectroscopy, photoionization, photodissociation, excited states, reactive intermediates.

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INSIGHTS INTO THE SOLVATO-/THERMO-PROMOTED INTRAMOLECULAR ELECTRON TRANSFER IN A TTF-σ-TCNQ DYAD WITH AN EXTREMELY LOW HOMO–LUMO GAP

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633612500393 ◽

2012 ◽

Vol 11 (03) ◽

pp. 599-609 ◽

Cited By ~ 5

Author(s):

YUHUA ZHOU ◽

KAI TAN ◽

XIN LU

Keyword(s):

Electron Transfer ◽

Gas Phase ◽

Ground State ◽

Polar Solvent ◽

Closed Shell ◽

Open Shell ◽

Polarizable Continuum Model ◽

Intramolecular Electron Transfer ◽

Singlet Ground State ◽

Solvent Polarization

The low-lying states of an organic donor-σ-acceptor dyad, i.e. tetrathiafulvalene-σ-tetracyano-p-quinodimethane (TTF-σ-TCNQ), in gas phase and in various solvents have been investigated by means of hybrid DFT calculations in combination with the conductor-like polarizable continuum model to describe solvent effects. It has been shown that the dyad, though preferring a closed-shell singlet ground state with an eclipsed conformation in gas phase, adopts the charge-separated zwitterionic states with an extended conformation (TTF+-σ-TCNQ-), i.e. open-shell singlet biradical ground state immediately followed by triplet biradical state, in polar solvent ( CH3CN and CH2Cl2 ) as a result of the intramolecular electron transfer (ET) stimulated by solvent polarization. The degree of such intramolecular ET is so strongly dependent on the polarity (dielectric constant) of solvent that the zwitterionic biradical states become more stable with respect to the closed-shell singlet state with increasing polarity of the solvent. As such, the dyad should show a higher ratio of biradicals in more polar solvent and/or at higher temperature and, hence, is chameleonic in nature.

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