Vibronic coupling of short‐lived electronic states

1986 ◽  
Vol 84 (1) ◽  
pp. 152-169 ◽  
Author(s):  
H. Estrada ◽  
L. S. Cederbaum ◽  
W. Domcke
Keyword(s):  
Electronic States ◽  
Vibronic Coupling

Vibronic Coupling. I. Mathematical Treatment for Two Electronic States

1961 ◽  
Vol 35 (3) ◽  
pp. 1059-1071 ◽  
Author(s):  
Robert L. Fulton ◽  
Martin Gouterman
Keyword(s):  
Electronic States ◽  
Vibronic Coupling ◽  
Mathematical Treatment

Vibronic coupling in the first four electronic states of CH2F+2

2015 ◽  
Vol 113 (19-20) ◽  
pp. 3073-3084 ◽  
Author(s):  
Rudraditya Sarkar ◽  
Susanta Mahapatra
Keyword(s):  
Electronic States ◽  
Vibronic Coupling

Analysis of vibronic coupling in a 4f molecular magnet with FIRMS

2021 ◽  
Author(s):  
Jon G. C. Kragskow ◽  
Jonathan Marbey ◽  
Christian Dirk Buch ◽  
Joscha Nehrkorn ◽  
Mykhaylo Ozerov ◽  
...  
Keyword(s):  
Magnetic Relaxation ◽  
Electronic States ◽  
Far Infrared ◽  
Vibronic Coupling ◽  
Chemical Processes ◽  
Molecular Magnets ◽  
Molecular Magnet ◽  
Magnetic Memory ◽  
Vibrational Modes ◽  
Phonon Coupling

<p><b>Vibronic coupling, the interaction between molecular vibrations and electronic states, is a pervasive effect that profoundly affects chemical processes. In the case of molecular magnetic materials, vibronic, or spin-phonon, coupling leads to magnetic relaxation, which equates to loss of magnetic memory and loss of phase coherence in molecular magnets and qubits, respectively. The study of vibronic coupling is challenging, and most experimental evidence is indirect. Here we employ far-infrared magnetospectroscopy to probe vibronic transitions in in [Yb(trensal)] (where H<sub>3</sub>trensal = 2,2,2-tris(salicylideneimino)trimethylamine). We find intense signals near electronic states, which we show arise due to an “envelope effect” in the vibronic coupling Hamiltonian, and we calculate the vibronic coupling fully <i>ab initio</i> to simulate the spectra. We subsequently show that vibronic coupling is strongest for vibrational modes that simultaneously distort the first coordination sphere and break the C<sub>3</sub> symmetry of the molecule. With this knowledge, vibrational modes could be identified and engineered to shift their energy towards or away from particular electronic states to alter their impact. Hence, these findings provide new insights towards developing general guidelines for the control of vibronic coupling in molecules.</b></p>

An analysis of vibronic coupling in the triplet absorption spectrum of pyrazine

1993 ◽  
Vol 71 (10) ◽  
pp. 1537-1547 ◽  
Author(s):  
Gad Fischer
Keyword(s):  
Theoretical Calculations ◽  
Electronic States ◽  
Emission Spectra ◽  
Vibronic Coupling ◽  
Triplet States ◽  
Model Calculations ◽  
Singlet States ◽  
Out Of Plane ◽  
Hot Band ◽  
Triplet Absorption

New measurements of the singlet–triplet [Formula: see text] absorption spectra of pyrazine and pyrazine-d4 at longer pathlengths and higher vapour pressures have been recorded. Particular attention was paid to the hot band region to the red of the electronic origin. The activities of the out-of-plane vibrations, υ4 and υ10a, were identified in sequence bands, and their triplet state vibrational frequencies were determined, 295 (276, -d4) and 254 (194, -d4) cm−1, respectively. Model calculations were undertaken to match the observed singlet and triplet absorption and emission spectra for vibronic coupling induced by (i) υ10a(b1g), and (ii) υ4 and υ5(b2g). The calculations allowed the ordering and the relative energies of the higher lying triplet states to be determined. The 3B2u and 3B1u electronic states are above the ground electronic state by about 3.9 and 4.4 eV, respectively. The ordering is in analogy with the corresponding singlet states but opposite to that predicted by most theoretical calculations.

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