@article{MazareiPenschkeSaalfrank2023,
  author    = {Mazarei, Elham and Penschke, Christopher and Saalfrank, Peter},
  title     = {Band gap engineering in two-dimensional materials by functionalization},
  series = {ACS Omega},
  volume    = {8},
  journal   = {ACS Omega},
  number    = {24},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {2470-1343},
  doi       = {10.1021/acsomega.3c02068},
  pages     = {22026 -- 22041},
  year      = {2023},
  abstract  = {Graphene is well-knownfor its unique combination of electricaland mechanical properties. However, its vanishing band gap limitsthe use of graphene in microelectronics. Covalent functionalizationof graphene has been a common approach to address this critical issueand introduce a band gap. In this Article, we systematically analyzethe functionalization of single-layer graphene (SLG) and bilayer graphene(BLG) with methyl (CH3) using periodic density functionaltheory (DFT) at the PBE+D3 level of theory. We also include a comparisonof methylated single-layer and bilayer graphene, as well as a discussionof different methylation options (radicalic, cationic, and anionic).For SLG, methyl coverages ranging from 1/8 to 1/1, (i.e.,the fully methylated analogue of graphane) are considered. We findthat up to a coverage theta of 1/2, graphene readily accepts CH3, with neighbor CH3 groups preferring trans positions. Above theta = 1/2, the tendency to accept further CH3 weakens and the lattice constant increases. The band gapbehaves less regularly, but overall it increases with increasing methylcoverage. Thus, methylated graphene shows potential for developingband gap-tuned microelectronics devices and may offer further functionalizationoptions. To guide in the interpretation of methylation experiments,vibrational signatures of various species are characterized by normal-modeanalysis (NMA), their vibrational density of states (VDOS), and infrared(IR) spectra, the latter two are obtained from ab initio moleculardynamics (AIMD) in combination with a velocity-velocity autocorrelationfunction (VVAF) approach.},
  language  = {en}
}
@article{MayerLeverPicconietal.2022,
  author    = {Mayer, Dennis and Lever, Fabiano and Picconi, David and Metje, Jan and Ališauskas, Skirmantas and Calegari, Francesca and D{\"u}sterer, Stefan and Ehlert, Christopher and Feifel, Raimund and Niebuhr, Mario and Manschwetus, Bastian and Kuhlmann, Marion and Mazza, Tommaso and Robinson, Matthew Scott and Squibb, Richard J. and Trabattoni, Andrea and Wallner, M{\aa}ns and Saalfrank, Peter and Wolf, Thomas J. A. and G{\"u}hr, Markus},
  title     = {Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy},
  series = {Nature communications},
  volume    = {13},
  journal   = {Nature communications},
  number    = {1},
  publisher = {Nature Research},
  address   = {Berlin},
  issn      = {2041-1723},
  doi       = {10.1038/s41467-021-27908-y},
  pages     = {9},
  year      = {2022},
  abstract  = {Imaging the charge flow in photoexcited molecules would provide key information on photophysical and photochemical processes. Here the authors demonstrate tracking in real time after photoexcitation the change in charge density at a specific site of 2-thiouracil using time-resolved X-ray photoelectron spectroscopy. The conversion of photon energy into other energetic forms in molecules is accompanied by charge moving on ultrafast timescales. We directly observe the charge motion at a specific site in an electronically excited molecule using time-resolved x-ray photoelectron spectroscopy (TR-XPS). We extend the concept of static chemical shift from conventional XPS by the excited-state chemical shift (ESCS), which is connected to the charge in the framework of a potential model. This allows us to invert TR-XPS spectra to the dynamic charge at a specific atom. We demonstrate the power of TR-XPS by using sulphur 2p-core-electron-emission probing to study the UV-excited dynamics of 2-thiouracil. The method allows us to discover that a major part of the population relaxes to the molecular ground state within 220-250 fs. In addition, a 250-fs oscillation, visible in the kinetic energy of the TR-XPS, reveals a coherent exchange of population among electronic states.},
  language  = {en}
}
@article{MelaniNagataSaalfrank2021,
  author    = {Melani, Giacomo and Nagata, Yuki and Saalfrank, Peter},
  title     = {Vibrational energy relaxation of interfacial OH on a water-covered alpha-Al2O3(0001) surface},
  series = {Physical chemistry, chemical physics : PCCP ; a journal of European chemical societies},
  volume    = {23},
  journal   = {Physical chemistry, chemical physics : PCCP ; a journal of European chemical societies},
  number    = {13},
  publisher = {Royal Society of Chemistry},
  address   = {Cambridge},
  issn      = {1463-9076},
  doi       = {10.1039/d0cp03777j},
  pages     = {7714 -- 7723},
  year      = {2021},
  abstract  = {Vibrational relaxation of adsorbates is a sensitive tool to probe energy transfer at gas/solid and liquid/solid interfaces. The most direct way to study relaxation dynamics uses time-resolved spectroscopy. Here we report on a non-equilibrium ab initio molecular dynamics (NE-AIMD) methodology to model vibrational relaxation of OH vibrations on a hydroxylated, water-covered alpha-Al2O3(0001) surface. In our NE-AIMD approach, after exciting selected O-H bonds their coupling to surface phonons and to the water adlayer is analyzed in detail, by following both the energy flow in time, as well as the time-evolution of Vibrational Density of States (VDOS) curves. The latter are obtained from Time-dependent Correlation Functions (TCFs) and serve as prototypical, generic representatives of time-resolved vibrational spectra. As most important results, (i) we find a few-picosecond lifetime of the excited modes and (ii) identify both hydrogen-bonded aluminols and water molecules in the adsorbed water layer as main dissipative channels, while the direct coupling to Al2O3 surface phonons is of minor importance on the timescales of interest. Our NE-AIMD/TCF methodology is powerful for complex adsorbate systems, in principle even reacting ones, and opens a way towards time-resolved vibrational spectroscopy.},
  language  = {en}
}
@article{KuntzeViljakkaTitovetal.2022,
  author    = {Kuntze, Kim and Viljakka, Jani and Titov, Evgenii and Ahmed, Zafar and Kalenius, Elina and Saalfrank, Peter and Priimagi, Arri},
  title     = {Towards low-energy-light-driven bistable photoswitches},
  series = {Photochemical \& photobiological sciences / European Society for Photobiology},
  volume    = {21},
  journal   = {Photochemical \& photobiological sciences / European Society for Photobiology},
  number    = {2},
  publisher = {Springer},
  address   = {Heidelberg},
  issn      = {1474-905X},
  doi       = {10.1007/s43630-021-00145-4},
  pages     = {159 -- 173},
  year      = {2022},
  abstract  = {Thermally stable photoswitches that are driven with low-energy light are rare, yet crucial for extending the applicability of photoresponsive molecules and materials towards, e.g., living systems. Combined ortho-fluorination and -amination couples high visible light absorptivity of o-aminoazobenzenes with the extraordinary bistability of o-fluoroazobenzenes. Herein, we report a library of easily accessible o-aminofluoroazobenzenes and establish structure-property relationships regarding spectral qualities, visible light isomerization efficiency and thermal stability of the cis-isomer with respect to the degree of o-substitution and choice of amino substituent. We rationalize the experimental results with quantum chemical calculations, revealing the nature of low-lying excited states and providing insight into thermal isomerization. The synthesized azobenzenes absorb at up to 600 nm and their thermal cis-lifetimes range from milliseconds to months. The most unique example can be driven from trans to cis with any wavelength from UV up to 595 nm, while still exhibiting a thermal cis-lifetime of 81 days. <br /> [GRAPHICS] <br /> .},
  language  = {en}
}
@article{YueMelaniKirschetal.2022,
  author    = {Yue, Yanhua and Melani, Giacomo and Kirsch, Harald and Paarmann, Alexander and Saalfrank, Peter and Campen, Richard Kramer and Tong, Yujin},
  title     = {Structure and Reactivity of a-Al2O3(0001) Surfaces: How Do Al-I and Gibbsite-like Terminations Interconvert?},
  series = {The journal of physical chemistry / publ. weekly by the American Chemical Society. C, Energy, materials, and catalysis},
  volume    = {126},
  journal   = {The journal of physical chemistry / publ. weekly by the American Chemical Society. C, Energy, materials, and catalysis},
  number    = {31},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {1932-7447},
  doi       = {10.1021/acs.jpcc.2c03743},
  pages     = {13467 -- 13476},
  year      = {2022},
  abstract  = {The alpha-Al2O3(0001) surface has been extensively studied because of its significance in both fundamental research and application. Prior work suggests that in ultra-high-vacuum (UHV), in the absence of water, the so-called Al-I termination is thermodynamically favored, while in ambient, in contact with liquid water, a Gibbsite-like layer is created. While the view of the alpha- Al2O3(0001)/H2O(l) interface appears relatively clear in theory, experimental characterization of this system has resulted in estimates of surface acidity, i.e., isoelectric points, that differ by 4 pH units and surface structure that in some reports has non-hydrogen-bonded surface aluminol (Al-OH) groups and in others does not. In this study, we employed vibrational sum frequency spectroscopy (VSFS) and density functional theory (DFT) simulation to study the surface phonon modes of the differently terminated alpha-Al2O3(0001) surfaces in both UHV and ambient. We find that, on either water dosing of the Al-I in UHV or heat-induced dehydroxylation of the Gibbsite-like in ambient, the surfaces do not interconvert. This observation offers a new explanation for disagreements in prior work on the alpha-Al2O3(0001)/liquid water interface -different preparation methods may create surfaces that do not interconvert-and shows that the surface phonon spectral response offers a novel probe of interfacial hydrogen bonding structure.},
  language  = {en}
}
@article{MullanMaschioSaalfranketal.2022,
  author    = {Mullan, Thomas and Maschio, Lorenzo and Saalfrank, Peter and Usvyat, Denis},
  title     = {Reaction barriers on non-conducting surfaces beyond periodic local MP2},
  series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr},
  volume    = {156},
  journal   = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr},
  number    = {7},
  publisher = {AIP Publishing},
  address   = {Melville},
  issn      = {0021-9606},
  doi       = {10.1063/5.0082805},
  pages     = {11},
  year      = {2022},
  abstract  = {The quest for "chemical accuracy" is becoming more and more demanded in the field of structure and kinetics of molecules at solid surfaces. In this paper, as an example, we focus on the barrier for hydrogen diffusion on a alpha-Al2O3 (0001) surface, aiming for a couple cluster singles, doubles, and perturbative triples [CCSD(T)]-level benchmark. We employ the density functional theory (DFT) optimized minimum and transition state structures reported by Heiden, Usvyat, and Saalfrank [J. Phys. Chem. C 123, 6675 (2019)]. The barrier is first evaluated at the periodic Hartree-Fock and local Moller-Plesset second-order perturbation (MP2) level of theory. The possible sources of errors are then analyzed, which includes basis set incompleteness error, frozen core, density fitting, local approximation errors, as well as the MP2 method error. Using periodic and embedded fragment models, corrections to these errors are evaluated. In particular, two corrections are found to be non-negligible (both from the chemical accuracy perspective and at the scale of the barrier value of 0.72 eV): the correction to the frozen core-approximation of 0.06 eV and the CCSD(T) correction of 0.07 eV. Our correlated wave function results are compared to barriers obtained from DFT. Among the tested DFT functionals, the best performing for this barrier is B3LYP-D3.},
  language  = {en}
}
@article{YangGhoshRoeseretal.2022,
  author    = {Yang, Jin and Ghosh, Samrat and Roeser, J{\´e}r{\^o}me and Acharjya, Amitava and Penschke, Christopher and Tsutsui, Yusuke and Rabeah, Jabor and Wang, Tianyi and Tameu, Simon Yves Djoko and Ye, Meng-Yang and Gr{\"u}neberg, Julia and Li, Shuang and Li, Changxia and Schomaecker, Reinhard and Van de Krol, Roel and Seki, Shu and Saalfrank, Peter and Thomas, Arne},
  title     = {Constitutional isomerism of the linkages in donor-acceptor covalent organic frameworks and its impact on photocatalysis},
  series = {Nature Communications},
  volume    = {13},
  journal   = {Nature Communications},
  number    = {1},
  publisher = {Nature Publishing Group UK},
  address   = {[London]},
  issn      = {2041-1723},
  doi       = {10.1038/s41467-022-33875-9},
  pages     = {10},
  year      = {2022},
  abstract  = {When new covalent organic frameworks (COFs) are designed, the main efforts are typically focused on selecting specific building blocks with certain geometries and properties to control the structure and function of the final COFs. The nature of the linkage (imine, boroxine, vinyl, etc.) between these building blocks naturally also defines their properties. However, besides the linkage type, the orientation, i.e., the constitutional isomerism of these linkages, has rarely been considered so far as an essential aspect. In this work, three pairs of constitutionally isomeric imine-linked donor-acceptor (D-A) COFs are synthesized, which are different in the orientation of the imine bonds (D-C=N-A (DCNA) and D-N=C-A (DNCA)). The constitutional isomers show substantial differences in their photophysical properties and consequently in their photocatalytic performance. Indeed, all DCNA COFs show enhanced photocatalytic H2 evolution performance than the corresponding DNCA COFs. Besides the imine COFs shown here, it can be concluded that the proposed concept of constitutional isomerism of linkages in COFs is quite universal and should be considered when designing and tuning the properties of COFs.},
  language  = {en}
}
@article{BouaklineSaalfrank2021,
  author    = {Bouakline, Foudhil and Saalfrank, Peter},
  title     = {Seemingly asymmetric atom-localized electronic densities following laser-dissociation of homonuclear diatomics},
  series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistry},
  volume    = {154},
  journal   = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistry},
  number    = {23},
  publisher = {American Institute of Physics},
  address   = {Melville},
  issn      = {0021-9606},
  doi       = {10.1063/5.0049710},
  pages     = {10},
  year      = {2021},
  abstract  = {Recent experiments on laser-dissociation of aligned homonuclear diatomic molecules show an asymmetric forward-backward (spatial) electron-localization along the laser polarization axis. Most theoretical models attribute this asymmetry to interference effects between gerade and ungerade vibronic states. Presumably due to alignment, these models neglect molecular rotations and hence infer an asymmetric (post-dissociation) charge distribution over the two identical nuclei. In this paper, we question the equivalence that is made between spatial electron-localization, observed in experiments, and atomic electron-localization, alluded by these theoretical models. We show that (seeming) agreement between these models and experiments is due to an unfortunate omission of nuclear permutation symmetry, i.e., quantum statistics. Enforcement of the latter requires mandatory inclusion of the molecular rotational degree of freedom, even for perfectly aligned molecules. Unlike previous interpretations, we ascribe spatial electron-localization to the laser creation of a rovibronic wavepacket that involves field-free molecular eigenstates with opposite space-inversion symmetry i.e., even and odd parity. Space-inversion symmetry breaking would then lead to an asymmetric distribution of the (space-fixed) electronic density over the forward and backward hemisphere. However, owing to the simultaneous coexistence of two indistinguishable molecular orientational isomers, our analytical and computational results show that the post-dissociation electronic density along a specified space-fixed axis is equally shared between the two identical nuclei-a result that is in perfect accordance with the principle of the indistinguishability of identical particles. Published under an exclusive license by AIP Publishing.},
  language  = {en}
}
@article{SchuermannTitovEbeletal.2022,
  author    = {Sch{\"u}rmann, Robin and Titov, Evgenii and Ebel, Kenny and Kogikoski Junior, Sergio and Mostafa, Amr and Saalfrank, Peter and Milosavljević, Aleksandar R. and Bald, Ilko},
  title     = {The electronic structure of the metal-organic interface of isolated ligand coated gold nanoparticles},
  series = {Nanoscale Advances},
  volume    = {4},
  journal   = {Nanoscale Advances},
  number    = {6},
  publisher = {Royal Society of Chemistry},
  address   = {Cambridge},
  issn      = {2516-0230},
  doi       = {10.1039/d1na00737h},
  pages     = {1599 -- 1607},
  year      = {2022},
  abstract  = {Light induced electron transfer reactions of molecules on the surface of noble metal nanoparticles (NPs) depend significantly on the electronic properties of the metal-organic interface. Hybridized metal-molecule states and dipoles at the interface alter the work function and facilitate or hinder electron transfer between the NPs and ligand. X-ray photoelectron spectroscopy (XPS) measurements of isolated AuNPs coated with thiolated ligands in a vacuum have been performed as a function of photon energy, and the depth dependent information of the metal-organic interface has been obtained. The role of surface dipoles in the XPS measurements of isolated ligand coated NPs is discussed and the binding energy of the Au 4f states is shifted by around 0.8 eV in the outer atomic layers of 4-nitrothiophenol coated AuNPs, facilitating electron transport towards the molecules. Moreover, the influence of the interface dipole depends significantly on the adsorbed ligand molecules. The present study paves the way towards the engineering of the electronic properties of the nanoparticle surface, which is of utmost importance for the application of plasmonic nanoparticles in the fields of heterogeneous catalysis and solar energy conversion.},
  language  = {en}
}
@article{FischerWertherBouaklineetal.2022,
  author    = {Fischer, Eric Wolfgang and Werther, Michael and Bouakline, Foudhil and Grossmann, Frank and Saalfrank, Peter},
  title     = {Non-Markovian vibrational relaxation dynamics at surfaces},
  series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr},
  volume    = {156},
  journal   = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr},
  number    = {21},
  publisher = {AIP Publishing},
  address   = {Melville},
  issn      = {0021-9606},
  doi       = {10.1063/5.0092836},
  pages     = {16},
  year      = {2022},
  abstract  = {Vibrational dynamics of adsorbates near surfaces plays both an important role for applied surface science and as a model lab for studying fundamental problems of open quantum systems. We employ a previously developed model for the relaxation of a D-Si-Si bending mode at a D:Si(100)-(2 x 1) surface, induced by a "bath " of more than 2000 phonon modes [Lorenz and P. Saalfrank, Chem. Phys. 482, 69 (2017)], to extend previous work along various directions. First, we use a Hierarchical Effective Mode (HEM) model [Fischer et al., J. Chem. Phys. 153, 064704 (2020)] to study relaxation of higher excited vibrational states than hitherto done by solving a high-dimensional system-bath time-dependent Schrodinger equation (TDSE). In the HEM approach, (many) real bath modes are replaced by (much less) effective bath modes. Accordingly, we are able to examine scaling laws for vibrational relaxation lifetimes for a realistic surface science problem. Second, we compare the performance of the multilayer multiconfigurational time-dependent Hartree (ML-MCTDH) approach with that of the recently developed coherent-state-based multi-Davydov-D2 Ansatz [Zhou et al., J. Chem. Phys. 143, 014113 (2015)]. Both approaches work well, with some computational advantages for the latter in the presented context. Third, we apply open-system density matrix theory in comparison with basically "exact " solutions of the multi-mode TDSEs. Specifically, we use an open-system Liouville-von Neumann (LvN) equation treating vibration-phonon coupling as Markovian dissipation in Lindblad form to quantify effects beyond the Born-Markov approximation. Published under an exclusive license by AIP Publishing.},
  language  = {en}
}