@article{AndrianovKlamrothSaalfranketal.2005, author = {Andrianov, Igor V. and Klamroth, Tillmann and Saalfrank, Peter and Bovensiepen, U. and Gahl, Cornelius and Wolf, M. M.}, title = {Quantum theoretical study of electron solvation dynamics in ice layers on a Cu(111) surface}, issn = {0021-9606}, year = {2005}, abstract = {Recent experiments using time- and angle-resolved two-photon photoemission (2PPE) spectroscopy at metal/polar adsorbate interfaces succeeded in time-dependent analysis of the process of electron solvation. A fully quantum mechanical, two-dimensional simulation of this process, which explicitly includes laser excitation, is presented here, confirming the origin of characteristic features, such as the experimental observation of an apparently negative dispersion. The inference of the spatial extent of the localized electron states from the angular dependence of the 2PPE spectra has been found to be non-trivial and system-dependent. (C) 2005 American Institute of Physics}, language = {en} } @article{AstMuellerFlehretal.2011, author = {Ast, Sandra and M{\"u}ller, Holger and Flehr, Roman and Klamroth, Tillmann and Walz, Bernd and Holdt, Hans-J{\"u}rgen}, title = {High Na+ and K+-induced fluorescence enhancement of a pi-conjugated phenylaza-18-crown-6-triazol-substituted coumarin fluoroionophore}, series = {Chemical communications}, volume = {47}, journal = {Chemical communications}, number = {16}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1359-7345}, doi = {10.1039/c0cc04370b}, pages = {4685 -- 4687}, year = {2011}, abstract = {The new pi-conjugated 1,2,3-triazol-1,4-diyl fluoroionophore 1 generated via Cu(I) catalyzed [3 + 2] cycloaddition shows high fluorescence enhancement factors (FEF) in the presence of Na+ (FEF = 58) and K+ (FEF = 27) in MeCN and high selectivity towards K+ under simulated physiological conditions (160 mM K+ or Na+, respectively) with a FEF of 2.5 for K+.}, language = {en} } @article{BalischewskiBhattacharyyaSperlichetal.2022, author = {Balischewski, Christian and Bhattacharyya, Biswajit and Sperlich, Eric and G{\"u}nter, Christina and Beqiraj, Alkit and Klamroth, Tillmann and Behrens, Karsten and Mies, Stefan and Kelling, Alexandra and Lubahn, Susanne and Holtzheimer, Lea and Nitschke, Anne and Taubert, Andreas}, title = {Tetrahalidometallate(II) ionic liquids with more than one metal}, series = {Chemistry - a European journal}, volume = {28}, journal = {Chemistry - a European journal}, number = {64}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1521-3765}, doi = {10.1002/chem.202201068}, pages = {13}, year = {2022}, abstract = {Fifteen N-butylpyridinium salts - five monometallic [C4Py](2)[MBr4] and ten bimetallic [C4Py](2)[(M0.5M0.5Br4)-M-a-Br-b] (M=Co, Cu, Mn, Ni, Zn) - were synthesized, and their structures and thermal and electrochemical properties were studied. All the compounds are ionic liquids (ILs) with melting points between 64 and 101 degrees C. Powder and single-crystal X-ray diffraction show that all ILs are isostructural. The electrochemical stability windows of the ILs are between 2 and 3 V. The conductivities at room temperature are between 10(-5) and 10(-6) S cm(-1). At elevated temperatures, the conductivities reach up to 10(-4) S cm(-1) at 70 degrees C. The structures and properties of the current bromide-based ILs were also compared with those of previous examples using chloride ligands, which illustrated differences and similarities between the two groups of ILs.}, language = {en} } @article{BedurkeKlamrothKrauseetal.2019, author = {Bedurke, Florian and Klamroth, Tillmann and Krause, Pascal and Saalfrank, Peter}, title = {Discriminating organic isomers by high harmonic generation}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {150}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, number = {23}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.5096473}, pages = {10}, year = {2019}, abstract = {High Harmonic Generation (HHG) is a nonlinear optical process that provides a tunable source for high-energy photons and ultrashort laser pulses. Recent experiments demonstrated that HHG spectroscopy may also be used as an analytical tool to discriminate between randomly oriented configurational isomers of polyatomic organic molecules, namely, between the cis- and trans-forms of 1,2-dichloroethene (DCE) [M. C. H. Wong et al., Phys. Rev. A 84, 051403 (2011)]. Here, we suggest as an economic and at the same time a reasonably accurate method to compute HHG spectra for polyatomic species, Time-Dependent Configuration Interaction Singles (TD-CIS) theory in combination with extended atomic orbital bases and different models to account for ionization losses. The HHG spectra are computed for aligned and unaligned cis- and trans-DCE. For the unaligned case, a coherent averaging over possible rotational orientations is introduced. Furthermore, using TD-CIS, possible differences between the HHG spectra of cis- and trans-DCE are studied. For aligned molecules, spectral differences between cis and trans emerge, which can be related to their different point group symmetries. For unaligned, randomly oriented molecules, we also find distinct HHG spectra in partial agreement with experiment. In addition to HHG response in the frequency space, we compute time-frequency HHG spectra to gain insight into which harmonics are emitted at which time. Further differences between the two isomers emerge, suggesting time-frequency HHG as another tool to discriminate configurational isomers.}, language = {en} } @article{BedurkeKlamrothSaalfrank2021, author = {Bedurke, Florian and Klamroth, Tillmann and Saalfrank, Peter}, title = {Many-electron dynamics in laser-driven molecules}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {23}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, number = {24}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/d1cp01100f}, pages = {13544 -- 13560}, year = {2021}, abstract = {With recent experimental advances in laser-driven electron dynamics in polyatomic molecules, the need arises for their reliable theoretical modelling. Among efficient, yet fairly accurate methods for many-electron dynamics are Time-Dependent Configuration Interaction Singles (TD-CIS) (a Wave Function Theory (WFT) method), and Real-Time Time-Dependent Density Functional Theory (RT-TD-DFT), respectively. Here we compare TD-CIS combined with extended Atomic Orbital (AO) bases, TD-CIS/AO, with RT-TD-DFT in a grid representation of the Kohn-Sham orbitals, RT-TD-DFT/Grid. Possible ionization losses are treated by complex absorbing potentials in energy space (for TD-CIS/AO) or real space (for RT-TD-DFT), respectively. The comparison is made for two test cases: (i) state-to-state transitions using resonant lasers (pi-pulses), i.e., bound electron motion, and (ii) large-amplitude electron motion leading to High Harmonic Generation (HHG). Test systems are a H-2 molecule and cis- and trans-1,2-dichlorethene, C2H2Cl2, (DCE). From time-dependent electronic energies, dipole moments and from HHG spectra, the following observations are made: first, for bound state-to-state transitions enforced by pi-pulses, TD-CIS nicely accounts for the expected population inversion in contrast to RT-TD-DFT, in agreement with earlier findings. Secondly, when using laser pulses under non-resonant conditions, dipole moments and lower harmonics in HHG spectra are obtained by TD-CIS/AO which are in good agreement with those obtained with RT-TD-DFT/Grid. Deviations become larger for higher harmonics and at low laser intensities, i.e., for low-intensity HHG signals. We also carefully test effects of basis sets for TD-CIS/AO and grid size for RT-TD-DFT/Grid, different exchange-correlation functionals in RT-TD-DFT, and absorbing boundaries. Finally, for the present examples, TD-CIS/AO is observed to be at least an order of magnitude more computationally efficient than RT-TD-DFT/Grid.}, language = {en} } @article{BronnerLeyssnerStremlauetal.2012, author = {Bronner, C. and Leyssner, F. and Stremlau, S. and Utecht, Manuel Martin and Saalfrank, Peter and Klamroth, Tillmann and Tegeder, P.}, title = {Electronic structure of a subnanometer wide bottom-up fabricated graphene nanoribbon: End states, band gap, and dispersion}, series = {Physical review : B, Condensed matter and materials physics}, volume = {86}, journal = {Physical review : B, Condensed matter and materials physics}, number = {8}, publisher = {American Physical Society}, address = {College Park}, issn = {1098-0121}, doi = {10.1103/PhysRevB.86.085444}, pages = {5}, year = {2012}, abstract = {Angle-resolved two-photon photoemission and high-resolution electron energy loss spectroscopy are employed to derive the electronic structure of a subnanometer atomically precise quasi-one-dimensional graphene nanoribbon (GNR) on Au(111). We resolved occupied and unoccupied electronic bands including their dispersion and determined the band gap, which possesses an unexpectedly large value of 5.1 eV. Supported by density functional theory calculations for the idealized infinite polymer and finite size oligomers, an unoccupied nondispersive electronic state with an energetic position in the middle of the band gap of the GNR could be identified. This state resides at both ends of the ribbon (end state) and is only found in the finite sized systems, i.e., the oligomers.}, language = {en} } @article{BronnerUtechtHaaseetal.2014, author = {Bronner, Christopher and Utecht, Manuel Martin and Haase, Anton and Saalfrank, Peter and Klamroth, Tillmann and Tegeder, Petra}, title = {Electronic structure changes during the surface-assisted formation of a graphene nanoribbon}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {140}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, number = {2}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.4858855}, pages = {7}, year = {2014}, abstract = {High conductivity and a tunability of the band gap make quasi-one-dimensional graphene nanoribbons (GNRs) highly interesting materials for the use in field effect transistors. Especially bottom-up fabricated GNRs possess well-defined edges which is important for the electronic structure and accordingly the band gap. In this study we investigate the formation of a sub-nanometer wide armchair GNR generated on a Au(111) surface. The on-surface synthesis is thermally activated and involves an intermediate non-aromatic polymer in which the molecular precursor forms polyanthrylene chains. Employing angle-resolved two-photon photoemission in combination with density functional theory calculations we find that the polymer exhibits two dispersing states which we attribute to the valence and the conduction band, respectively. While the band gap of the non-aromatic polymer obtained in this way is relatively large, namely 5.25 +/- 0.06 eV, the gap of the corresponding aromatic GNR is strongly reduced which we attribute to the different degree of electron delocalization in the two systems.}, language = {en} } @article{EhlertKlamroth2017, author = {Ehlert, Christopher and Klamroth, Tillmann}, title = {The quest for best suited references for configuration interaction singles calculations of core excited states}, series = {Journal of computational chemistry : organic, inorganic, physical, biological}, volume = {38}, journal = {Journal of computational chemistry : organic, inorganic, physical, biological}, publisher = {Wiley-Blackwell}, address = {Hoboken}, issn = {0192-8651}, doi = {10.1002/jcc.24531}, pages = {116 -- 126}, year = {2017}, abstract = {Near edge X-ray absorption fine structure (NEXAFS) simulations based on the conventional configuration interaction singles (CIS) lead to excitation energies, which are systematically blue shifted. Using a (restricted) open shell core hole reference instead of the Hartree Fock (HF) ground state orbitals improves (Decleva et al., Chem. Phys., 1992, 168, 51) excitation energies and the shape of the spectra significantly. In this work, we systematically vary the underlying SCF approaches, that is, based on HF or density functional theory, to identify best suited reference orbitals using a series of small test molecules. We compare the energies of the K edges and NEXAFS spectra to experimental data. The main improvement compared to conventional CIS, that is, using HF ground state orbitals, is due to the electrostatic influence of the core hole. Different SCF approaches, density functionals, or the use of fractional occupations lead only to comparably small changes. Furthermore, to account for bigger systems, we adapt the core-valence separation for our approach. We demonstrate that the good quality of the spectrum is not influenced by this approximation when used together with the non-separated ground state wave function. Simultaneously, the computational demands are reduced remarkably. (C) 2016 Wiley Periodicals, Inc.}, language = {en} } @article{EhlertKlamroth2020, author = {Ehlert, Christopher and Klamroth, Tillmann}, title = {PSIXAS: A Psi4 plugin for efficient simulations of X-ray absorption spectra based on the transition-potential and Delta-Kohn-Sham method}, series = {Journal of computational chemistry : organic, inorganic, physical, biological}, volume = {41}, journal = {Journal of computational chemistry : organic, inorganic, physical, biological}, number = {19}, publisher = {Wiley}, address = {Hoboken}, issn = {0192-8651}, doi = {10.1002/jcc.26219}, pages = {1781 -- 1789}, year = {2020}, abstract = {Near edge X-ray absorption fine structure (NEXAFS) spectra and their pump-probe extension (PP-NEXAFS) offer insights into valence- and core-excited states. We present PSIXAS, a recent implementation for simulating NEXAFS and PP-NEXAFS spectra by means of the transition-potential and the Delta-Kohn-Sham method. The approach is implemented in form of a software plugin for the Psi4 code, which provides access to a wide selection of basis sets as well as density functionals. We briefly outline the theoretical foundation and the key aspects of the plugin. Then, we use the plugin to simulate PP-NEXAFS spectra of thymine, a system already investigated by others and us. It is found that larger, extended basis sets are needed to obtain more accurate absolute resonance positions. We further demonstrate that, in contrast to ordinary NEXAFS simulations, where the choice of the density functional plays a minor role for the shape of the spectrum, for PP-NEXAFS simulations the choice of the density functional is important. Especially hybrid functionals (which could not be used straightforwardly before to simulate PP-NEXAFS spectra) and their amount of "Hartree-Fock like" exact exchange affects relative resonance positions in the spectrum.}, language = {en} } @article{FarraThielWinteretal.2011, author = {Farra, Ramzi and Thiel, Kerstin and Winter, Alette and Klamroth, Tillmann and Poeppl, Andreas and Kelling, Alexandra and Schilde, Uwe and Taubert, Andreas and Strauch, Peter}, title = {Tetrahalidocuprates(II)-structure and EPR spectroscopy Part 1: Tetrabromidocuprates(II)}, series = {New journal of chemistry}, volume = {35}, journal = {New journal of chemistry}, number = {12}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1144-0546}, doi = {10.1039/c1nj20271e}, pages = {2793 -- 2803}, year = {2011}, abstract = {Tetrahalidocuprates(II) show a high degree of structural flexibility. We present the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of four new tetrabromidocuprate(II) compounds and compare the results with previously reported data. The cations in the new compounds are the sterically demanding benzyltriphenylphosphonium, methyltriphenylphosphonium, tetraphenylphosphonium, and hexadecyltrimethylammonium ions; they were used to achieve a reasonable separation of the paramagnetic Cu(II) ions for EPR spectroscopy. X-Ray crystallography shows that in all four complexes the [CuBr4](2-) units have a distorted tetrahedral coordination geometry which is in agreement with DFT calculations. The EPR hyperfine structure was not resolved. This is due to the exchange broadening resulting from still incomplete separation of the paramagnetic Cu(II) centres. Nevertheless, the principal values of the electron Zeemann tensor (g(parallel to) and g(perpendicular to)) of the complexes could be determined. A correlation of structural (X-ray) parameters with the spin density at the copper centres (DFT) is well reflected in the EPR spectra of the bromidocuprates. This enables the correlation of X-ray and EPR parameters to predict the structure of tetrabromidocuprates in physical states other than the crystalline state. As a result, we provide a method to structurally characterize [CuBr4](2-) in, for example, ionic liquids or in solution, which has important implications for e.g. catalysis or materials science.}, language = {en} }