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Vibronic Coupling in Molecules and in Solids

✍ Scribed by Wojciech Grochala; Roald Hoffmann; Peter P. Edwards


Publisher
John Wiley and Sons
Year
2003
Tongue
English
Weight
238 KB
Volume
9
Category
Article
ISSN
0947-6539

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✦ Synopsis


We utilize the experience gained in our previous studies on the "chemistry of vibronic coupling" in simple homonuclear and heteronuclear molecules to begin assembling theoretical guidelines for the construction of potentially superconducting solids exhibiting large electron-phonon coupling. For this purpose we analyze similarities between vibronic coupling in isolated molecules and in extended solids. In particular, we study vibronic coupling along the antisymmetric stretch coordinate (Q(as)) in linear symmetric AAA molecules, and along the optical phonon "pairing" mode coordinate (Q(opt)) in corresponding one-dimensional A chains built of equidistant A atoms. This is done for a broad range of chemical elements (A). The following similarities between vibronic coupling in molecules and phonon coupling in solids emerge from our calculations: 1) The HOMO/LUMO electronic energy gap in an AAA molecule increases along Q(as), and the highest occupied crystal orbital/lowest unoccupied crystal orbital gap in A chain increases along Q(opt). 2) The maximum vibronic instability is invariably obtained for a half-filled, singly occupied molecular orbital in AAA molecules, and for a corresponding half-filled band in A chains. 3) The vibronic stability of an AAA molecule increases with a decrease of the AA bond length, as does the vibronic stability of A chains (external pressure may lead to a reversal of a Peierls distortion). 4) The high degree of s-p mixing and ionic/covalent forbidden curve crossing dramatically enhance the vibronic instability of both AAA molecules and A chains. We also introduce one quantitative relationship: The parameter log(R) (where R is molar refractivity, a parameter used by Herzfeld to prescribe the conditions for the metallization of the elements) correlates with a parameter f(AA) (defined as twice the electronegativity of A, divided by the equilibrium AA bond length), used by two of us previously to describe vibronic coupling in AAA molecules for a broad range of elements (A=halogen, H, or an alkali metal). We hope to illustrate that key chemical aspects of vibronic coupling in simple molecules may thus be profitably transferred to corresponding materials in the solid state.


πŸ“œ SIMILAR VOLUMES


Vibronic coupling and line broadening in
✍ G. Orlandi; W. Siebrand πŸ“‚ Article πŸ“… 1971 πŸ› Elsevier Science 🌐 English βš– 327 KB

The vibronic coupling between quasi-degenerate adiabatic Born-Oppenheimer states is calculated without using the Herzberg-Teller perturbation expansion, and is shown to be strongly dependent on the model chosen.

Weak and strong vibronic coupling limits
✍ Willem Siebrand; Marek Z. Zgierski πŸ“‚ Article πŸ“… 1976 πŸ› Elsevier Science 🌐 English βš– 387 KB

AR exactly solvable vibronic coupling model is used to improve existing definitions of strong and weak vibronic coupling Limits in molecules and to derive a unique correlation between the corresponding energy Icvels. \* Is&d as NRCC No. 15073.

Interaction between vibronic coupling an
✍ Willem Siebrand; Marek Z. Zgierski πŸ“‚ Article πŸ“… 1979 πŸ› Elsevier Science 🌐 English βš– 308 KB

The intensity distribution in progressions of the big mode observed in phosphcrescence and phosphorescence-excitation spectra of p) mzine is interprered m terms of a model mvohin~ vrbronic couplin: in both singlet and triplet manifolds mediated by spin-orbit coupling. Pyrazine has been used repeated

Vibronic coupling in the benzyl radical
✍ Giorgio Orlandi; Gabriella Poggi; Francesco Zerbetto πŸ“‚ Article πŸ“… 1985 πŸ› Elsevier Science 🌐 English βš– 492 KB

The vlbromc pcrturbatlons among the lowest cxnted states of bcnzyl, computed by a CNDO/S program in the floaung-orbltal scheme, are presented. The psb (v,sb) modes are the tqbrations that most strongly (weakly) couple (he quandcgcncratc lAz and 2& states. The rcsulls arc rclcvant to the inlcrprelati