New method of accurate estimation of the electron–phonon coupling constants in fractionally charged incommensurate electronic states in molecular systems

Abstract

The electron-phonon interactions in the fractionally positively charged incommensurate tetrathiafulvalene (TTF) molecular systems are investigated. In particular, since there are fractionally positive charges per TTF molecule, it is very difficult to estimate the vibronic and electron-phonon coupling constants, and thus there have been no reports of the exact calculations in the electron-phonon coupling constants in such fractionally positively charged incommensurate systems. Therefore, in this paper, we suggest new method of accurate estimation of the electron-phonon coupling constants in the fractionally positively charged systems. Total electron-phonon coupling constants for the monocation (l(+100)) of TTF is compared with that for the monoanion (l(-100)) of tetracyanoquinodimethanide (TCNQ). Furthermore, logarithmically averaged phonon frequency for the monocation (ν(ln , +1.00)) of TTF is compared with that for the monoanion (ν(ln , -1.00)) of TCNQ. The C-C and C-S stretching mode of 1599 cm(-1) and the C-S-C and C-C-S bending mode of 472 cm(-1) strongly couple to the b(3)u highest occupied molecular orbital (HOMO) in TTF molecule. The l(+100) value for TTF molecule is estimated to be 0.274 eV, and the ν(ln , +1.00) value for TTF molecule is estimated to be 926 cm(-1). The density of states at the Fermi level (N(NM, crystal)(ε(F))(+0.59, +0.59)) values for TTF(0.59+), which are essential physical values in order to investigate the mechanisms of the non-Ohmic current-voltage characteristics excellently suggested by Cohen and Heeger et al., are also estimated. By comparing the N(NM, crystal)(ε(F))(+0.59, +0.59) values estimated by us with those estimated from the experimental results of the Pauli susceptibility and the current-voltage characteristics in TTF(0.59+) suggested by Cohen and Heeger et al., and from the band calculations, we show that the l(+0.59), ν(ln , +1.00), RE(+0.59), and N(NM, crystal)(ε(F))(+0.59, +0.59) values estimated by our new calculation method are very accurate and reliable.