TY  - JOUR
A1  - Floss, Gereon
A1  - Granucci, Giovanni
A1  - Saalfrank, Peter
T1  - Surface hopping dynamics of direct trans -> cis photoswitching of an azobenzene derivative in constrained adsorbate geometries
JF  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
N2  - With ongoing miniaturization of electronic devices, the need for individually addressable, switchable molecules arises. An example are azobenzenes on surfaces which have been shown to be switchable between trans and cis forms. Here, we examine the "direct" (rather than substrate-mediated) channel of the trans -> cis photoisomerization after pi pi* excitation of tetra-tert-butyl-azobenzene physisorbed on surfaces mimicking Au(111) and Bi(111), respectively. In spirit of the direct channel, the electronic structure of the surface is neglected, the latter merely acting as a rigid platform which weakly interacts with the molecule via Van-der-Waals forces. Starting from thermal ensembles which represent the trans-form, sudden excitations promote the molecules to pi pi*-excited states which are non-adiabatically coupled among themselves and to a n pi*-excited and the ground state, respectively. After excitation, relaxation to the ground state by internal conversion takes place, possibly accompanied by isomerization. The process is described here by "on the fly" semiclassical surface hopping dynamics in conjunction with a semiempirical Hamiltonian (AM1) and configuration-interaction type methods. It is found that steric constraints imposed by the substrate lead to reduced but non-vanishing, trans -> cis reaction yields and longer internal conversion times than for the isolated molecule. Implications for recent experiments for azobenzenes on surfaces are discussed.
KW  - AM1 calculations
KW  - bismuth
KW  - configuration interactions
KW  - excited states
KW  - gold
KW  - isomerisation
KW  - organic compounds
KW  - photochemistry
KW  - van der Waals forces
Y1  - 2012
U6  - https://doi.org/10.1063/1.4769087
SN  - 0021-9606
VL  - 137
IS  - 23
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Krivenkov, Maxim
A1  - Marchenko, Dimitry
A1  - Sánchez-Barriga, Jaime
A1  - Golias, Evangelos
A1  - Rader, Oliver
A1  - Varykhalov, Andrei
T1  - Origin of the band gap in Bi-intercalated graphene on Ir(111)
JF  - 2D Materials
N2  - Proximity to heavy sp-elements is considered promising for reaching a band gap in graphene that could host quantum spin Hall states. The recent report of an induced spin-orbit gap of 0.2 eV in Pb-intercalated graphene detectable by spin-resolved photoemission has spurred renewed interest in such systems (Klimovskikh et al 2017 ACS Nano 11, 368). In the case of Bi intercalation an even larger band gap of 0.4 eV has been observed but was assigned to the influence of a dislocation network (Warmuth et al 2016 Phys. Rev. B 93, 165 437). Here, we study Bi intercalation under graphene on Ir(111) and report a nearly ideal graphene dispersion without band replicas and no indication of hybridization with the substrate. The band gap is small (0.19 eV) and can be tuned by +/- 25 meV through the Bi coverage. The Bi atomic density is higher than in the recent report. By spin-resolved photoemission we exclude induced spin-orbit interaction as origin of the gap. Quantitative agreement of a photoemission intensity analysis with the measured band gap suggests sublattice symmetry breaking as one of the possible band gap opening mechanisms. We test several Bi structures by density functional theory. Our results indicate the possibility that Bi intercalates in the phase of bismuthene forming a graphene-bismuthene van der Waals heterostructure.
KW  - graphene
KW  - bismuth
KW  - Ir(111)
KW  - spin-orbit interaction
KW  - ARPES
KW  - STM
KW  - bismuthene
Y1  - 2021
U6  - https://doi.org/10.1088/2053-1583/abd1e4
SN  - 2053-1583
VL  - 8
IS  - 3
PB  - IOP Publ. Ltd.
CY  - Bristol
ER  -