One of the key predictions of the diabatic state picture of hydrogen bonding is that there should be an excited electronic state (a twin state) which is the "anti-bonding" combination of the two diabatic states associated with the ground state H-bond.
Recently, I posted about a possible identification of this state in malonaldehyde.
The following recent paper is relevant.
Symmetry breaking in the axial symmetrical configurations of enolic propanedial, propanedithial, and propanediselenal: pseudo Jahn–Teller effect versus the resonance-assisted hydrogen bond theory
Elahe Jalali, Davood Nori-Shargh
The key figure is below. The lowest B2 state is the twin state.
In the diabatic state picture, Delta is half of the off-diagonal matrix element that couples the two diabatic states.
Similar diagrams occur when O is replaced with S or Se.
The paper does not discuss twin states, but interprets everything in terms of the framework of the
(A1 + B2) ⊗ b2 pseudo-Jahn-Teller effect.
Two minor issues might be raised about this work.
It uses TD-DFT (Time-dependent Density Functional Theory). It is contentious how reliable that is for excited states in organic molecules.
The diabatic states are not explicitly constructed.
These issues could be addressed by using higher level quantum chemistry and constructing the diabatic states by a systematic procedure, as was done by Seth Olsen for a family of methine dye molecules.
Subscribe to:
Post Comments (Atom)
From Leo Szilard to the Tasmanian wilderness
Richard Flanagan is an esteemed Australian writer. My son recently gave our family a copy of Flanagan's recent book, Question 7 . It is...
-
Is it something to do with breakdown of the Born-Oppenheimer approximation? In molecular spectroscopy you occasionally hear this term thro...
-
If you look on the arXiv and in Nature journals there is a continuing stream of people claiming to observe superconductivity in some new mat...
-
I welcome discussion on this point. I don't think it is as sensitive or as important a topic as the author order on papers. With rega...
No comments:
Post a Comment