ChemInform Abstract: PHOTOELECTRON SPECTRUM AND ELECTRONIC STRUCTURE OF TETRATHIOFULVALENE (TTF)

Recently we reported the results of some semiempirical and ab initio studies in which we compared the electronic structure of the hitherto unknown borinine with those of benzene and pyridine. The results of our calculations led us to the conclusion that the elusive nature of borabenzene is caused by its high reactivity, which might at least in part be due to the pronounced σ acceptor properties of a low-lying σ* molecular orbital.We now present the results of further ab initio and semiempirical (MNDO) investigations in which we performed full geometry optimizations for the molecule using two different basis sets (STO-3G, 4-31G) and also calculated the vibrational spectra of the 10B and 11B isotopomeric borabenzene molecules at the 4-31 G level of ab initio theory and with the semiempirical MNDO method.The calculated vibrational spectrum might be helpful to the experimentalist in identifying the molecule, for example trapped in a rare gas matrix among the side products.The calculated orbital energies can be useful in identifying the molecule by means of its photoelectron spectrum.

Download Full-text

Valence electronic structure of [EMIM][B(CN)4]: ion-pair vs. bulk description

RSC Advances ◽

10.1039/c9ra06762k ◽

2019 ◽

Vol 9 (57) ◽

pp. 33140-33146 ◽

Cited By ~ 1

Author(s):

I. Kuusik ◽

M. Berholts ◽

J. Kruusma ◽

A. Tõnisoo ◽

E. Lust ◽

...

Keyword(s):

Ionic Liquid ◽

Electronic Structure ◽

Ab Initio ◽

Photoelectron Spectrum ◽

Ion Pair ◽

Calculation Methods ◽

Valence Electronic Structure

The ultraviolet photoelectron spectrum of the [EMIM][B(CN)4] ionic liquid was recorded and simulated using different ab initio ion-pair and bulk calculation methods.

Download Full-text

Photoelectron Spectrum and Electronic Structure of Tetrathiofulvalene (TTF)

Canadian Journal of Chemistry ◽

10.1139/v74-497 ◽

1974 ◽

Vol 52 (19) ◽

pp. 3373-3377 ◽

Cited By ~ 25

Author(s):

A. John Berlinsky ◽

James F. Carolan ◽

Larry Weiler

Keyword(s):

Electronic Structure ◽

Band Structure ◽

Molecular Orbital ◽

Photoelectron Spectrum ◽

Crystal Packing ◽

Ionization Potentials ◽

Photoelectron Spectra ◽

Molecular Orbital Calculations ◽

Conducting Salt

The electronic structure of tetrathiofulvalene (TTF) has been determined from its photoelectron spectrum and the photoelectron data for the tetrahydro derivative of TTF and 1,3-dithiolane. Correlations of the ionization potentials (i.p.) and several molecular orbital calculations are used in the assignment of the photoelectron spectra of these three compounds. The first five i.p. of TTF and their assignment are as follows: 6.92 (3b1u), 8.67 (2b2g), 9.73 (2b1u), 10.16 (au) and 10.49 eV (b3g). The sixth i.p. at 11.00 eV is tentatively assigned to the 1b2g level. The electronic structure of TTF is important in understanding the crystal packing and band structure of the highly conducting salt, TTF•TCNQ.

Download Full-text