@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} } @article{FlossKlamrothSaalfrank2011, author = {Floss, Gereon and Klamroth, Tillmann and Saalfrank, Peter}, title = {Laser-controlled switching of molecular arrays in an dissipative environment}, series = {Physical review : B, Condensed matter and materials physics}, volume = {83}, journal = {Physical review : B, Condensed matter and materials physics}, number = {10}, publisher = {American Physical Society}, address = {College Park}, issn = {1098-0121}, doi = {10.1103/PhysRevB.83.104301}, pages = {9}, year = {2011}, abstract = {The optical switching of molecular ensembles in a dissipative environment is a subject of various fields of chemical physics and physical chemistry. Here we try to switch arrays of molecules from a stable collective ground state to a state in which all molecules have been transferred to another stable higher-energy configuration. In our model switching proceeds through electronically excited intermediates which are coherently coupled to each other through dipolar interactions, and which decay incoherently within a finite lifetime by coupling to a dissipative environment. The model is quite general, but parameters are chosen to roughly resemble the all-trans -> all-cis isomerization of an array of azobenzene molecules on a surface. Using analytical and optimal control pulses and the concept of "laser distillation," we demonstrate that for various aggregates (dimers up to hexamers), controlled and complete switching should be possible.}, language = {en} } @article{FuechselKlamrothDokicetal.2006, author = {F{\"u}chsel, Gernot and Klamroth, Tillmann and Dokic, Jadranka and Saalfrank, Peter}, title = {On the electronic structure of neutral and ionic azobenzenes and their possible role as surface mounted molecular switches}, series = {The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces \& biophysical chemistry}, volume = {110}, journal = {The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces \& biophysical chemistry}, number = {33}, publisher = {Soc.}, address = {Washington}, issn = {1520-6106}, doi = {10.1021/jp060969v}, pages = {16337 -- 16345}, year = {2006}, abstract = {We report quantum chemical calculations, mostly based on density functional theory, on azobenzene and substituted azobenzenes as neutral molecules or ions, in ground and excited states. Both the cis and trans configurations are computed as well as the activation energies to transform one isomer into the other and the possible reaction paths and reaction surfaces along the torsion and inversion modes. All calculations are done for the isolated species, but results are discussed in light of recent experiments aiming at the switching of surface mounted azobenzenes by scanning tunneling microscopes.}, language = {en} } @article{FuechselKlamrothMonturetetal.2011, author = {F{\"u}chsel, Gernot and Klamroth, Tillmann and Monturet, Serge and Saalfrank, Peter}, title = {Dissipative dynamics within the electronic friction approach the femtosecond laser desorption of H-2/D-2 from Ru(0001)}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {13}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, number = {19}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c0cp02086a}, pages = {8659 -- 8670}, year = {2011}, abstract = {An electronic friction approach based on Langevin dynamics is used to describe the multidimensional (six-dimensional) dynamics of femtosecond laser induced desorption of H-2 and D-2 from a H(D)-covered Ru(0001) surface. The paper extends previous reduced-dimensional models, using a similar approach. In the present treatment forces and frictional coefficients are calculated from periodic density functional theory (DFT) and essentially parameter-free, while the action of femtosecond laser pulses on the metal surface is treated by using the two-temperature model. Our calculations shed light on the performance and validity of various adiabatic, non-adiabatic, and Arrhenius/Kramers type kinetic models to describe hot-electron mediated photoreactions at metal surfaces. The multidimensional frictional dynamics are able to reproduce and explain known experimental facts, such as strong isotope effects, scaling of properties with laser fluence, and non-equipartitioning of vibrational, rotational, and translational energies of desorbing species. Further, detailed predictions regarding translations are made, and the question for the controllability of photoreactions at surfaces with the help of vibrational preexcitation is addressed.}, language = {en} } @article{FuechselKlamrothTremblayetal.2010, author = {F{\"u}chsel, Gernot and Klamroth, Tillmann and Tremblay, Jean Christophe and Saalfrank, Peter}, title = {Stochastic approach to laser-induced ultrafast dynamics : the desorption of H-2/D-2 from Ru(0001)}, issn = {1463-9076}, doi = {10.1039/C0cp00895h}, year = {2010}, abstract = {The desorption of molecular hydrogen and deuterium induced by femtosecond-laser pulses is studied theoretically for the so-called DIMET (Desorption Induced by Multiple Electronic Transitions) process. These investigations are based on nonadiabatic classical Monte Carlo trajectory (CMCT) simulations on a ground and an excited state potential energy surface, including up to all six adsorbate degrees of freedom. The focus is on the hot-electron mediated energy transfer from the surface to the molecule and back, and the energy partitioning between the different degrees of freedom of the desorbing molecules. We first validate for a two-mode model comprising the desorption mode and the internal vibrational coordinate, the classical Monte Carlo trajectory method by comparing with Monte Carlo wavepacket (MCWP) calculations arising from a fully quantum mechanical open-system density matrix treatment. We then proceed by extending the CMCT calculations to include all six nuclear degrees of freedom of the desorbing molecule. This allows for a detailed comparison between theory and experiment concerning isotope effects, energy partitioning (translational, vibrational, and rotational energies and their distributions), and the dependence of these properties on the laser fluence. The most important findings are as follows. (i) CMCT agrees qualitative with the MCWP scheme. (ii) The basic experimental features such as the large isotope effect, the non-linear increase of yield with laser fluence, translationally hot products (in the order of several 1000 K) and non-equipartitioning of translational and internal energies (E-trans > E- vib > E-rot) are well reproduced. (iii) Predictions concerning a strong angular dependence of translational energies at large observation angles are also made.}, language = {en} } @article{FuechselTremblayKlamrothetal.2012, author = {F{\"u}chsel, Gernot and Tremblay, Jean Christophe and Klamroth, Tillmann and Saalfrank, Peter}, title = {Selective excitation of molecule-surface vibrations in H2 and D2 dissociatively adsorbed on Ru(0001)}, series = {Israel journal of chemistry}, volume = {52}, journal = {Israel journal of chemistry}, number = {5}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0021-2148}, doi = {10.1002/ijch.201100097}, pages = {438 -- 451}, year = {2012}, abstract = {In this contribution we report about the selective vibrational excitation of H2 and D2 on Ru(0001) as an example for nonadiabatic coupling of an open quantum system to a dissipative environment. We investigate the possibility of achieving state-selective vibrational excitations of H2 and D2 adsorbed on a Ru(0001) surface using picosecond infrared laser pulses. The systems behavior is explored using pulses that are rationally designed and others that are optimized using a time-local variant of Optimal Control Theory. The effects of dissipation on the laser-driven dynamics are studied using the reduced-density matrix formalism. The non-adiabatic couplings between adsorbate and surface are computed perturbatively, for which our recently introduced state-resolved anharmonic rate model is used. It is shown that mode- and state-selective excitation can be achieved in the absence of dissipation when using optimized laser pulses. The inclusion of dissipation in the model reduces the state selectivity and the population transfer yield to highly excited states. In this case, mode activation is most effectively realized by a rational pulse of carefully chosen duration rather than by a locally optimized pulse.}, language = {en} } @article{FuechselTremblayKlamrothetal.2013, author = {F{\"u}chsel, Gernot and Tremblay, Jean Christophe and Klamroth, Tillmann and Saalfrank, Peter}, title = {Quantum dynamical simulations of the femtosecond-laser-induced ultrafast desorption of H2 and D2 from Ru(0001)}, series = {ChemPhysChem : a European journal of chemical physics and physical chemistry}, volume = {14}, journal = {ChemPhysChem : a European journal of chemical physics and physical chemistry}, number = {7}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1439-4235}, doi = {10.1002/cphc.201200940}, pages = {1471 -- 1478}, year = {2013}, abstract = {We investigate the recombinative desorption of hydrogen and deuterium from a Ru(0001) surface initiated by femtosecond laser pulses. We adopt a quantum mechanical two-state model including three molecular degrees of freedom to describe the dynamics within the desorption induced by electronic transition (DIET) limit. The energy distributions as well as the state-resolved and ensemble properties of the desorbed molecules are analyzed in detail by using the time-energy method. Our results shed light on the experimentally observed 1) large isotopic effects regarding desorption yields and translational energies and 2) the nonequal energy partitioning into internal and translational modes. In particular, it is shown that a single temperature is sufficient to characterize the energy distributions for all degrees of freedom. Further, we confirm that quantization effects play an important role in the determination of the energy partitioning.}, language = {en} } @article{FuechselTremblayKlamrothetal.2012, author = {F{\"u}chsel, Gernot and Tremblay, Jean Christophe and Klamroth, Tillmann and Saalfrank, Peter and Frischkorn, C.}, title = {Concept of a single temperature for highly nonequilibrium laser-induced hydrogen desorption from a ruthenium surface}, series = {Physical review letters}, volume = {109}, journal = {Physical review letters}, number = {9}, publisher = {American Physical Society}, address = {College Park}, issn = {0031-9007}, doi = {10.1103/PhysRevLett.109.098303}, pages = {5}, year = {2012}, abstract = {Laser-induced condensed phase reactions are often interpreted as nonequilibrium phenomena that go beyond conventional thermodynamics. Here, we show by Langevin dynamics and for the example of femtosecond-laser desorption of hydrogen from a ruthenium surface that light adsorbates thermalize rapidly due to ultrafast energy redistribution after laser excitation. Despite the complex reaction mechanism involving hot electrons in the surface region, all desorption product properties are characterized by equilibrium distributions associated with a single, unique temperature. This represents an example of ultrahot chemistry on the subpicosecond time scale.}, language = {en} } @article{GaebelBeinMathaueretal.2021, author = {Gaebel, Tina and Bein, Daniel and Mathauer, Daniel and Utecht, Manuel and Palmer, Richard E. and Klamroth, Tillmann}, title = {Nonlocal STM manipulation of chlorobenzene on Si(111)-7 x 7}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {125}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {22}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.1c02612}, pages = {12175 -- 12184}, year = {2021}, abstract = {We use quantum chemical cluster models together with constrained density STM Ph CI functional theory (DFT) and ab initio molecular dynamics (AIMD) for open system to simulate tip and rationalize nonlocal scanning tunneling microscope (STM) manipulation experiments for Philh ci chlorobenzene (PhCl) on a Si(111)-7 X 7 surface. We consider three different processes, namely, the electron-induced dissociation of the carbon-chlorine bond for physisorbed PhCl molecules at low temperatures and the electron- or hole-induced desorption of chemisorbed PhCl at 300 K. All processes can be induced nonlocally, i.e., up to several nanometers (nm) away from the injection site, in STM experiments. We rationalize and explain the experimental findings regarding the STM-induced dissociation using constrained DFT. The coupling of STM-induced ion resonances to nuclear degrees of freedom is simulated with AIMD using the Gadzuk averaging approach for open systems. From this data, we predict a 4 fs lifetime for the cationic resonance. For the anion model, desorption could not be observed. In addition, the same cluster models are used for transition-state theory calculations, which are compared to and validated against time-lapse STM experiments.}, language = {en} } @article{HuberKlamroth2005, author = {Huber, C. and Klamroth, Tillmann}, title = {Simulation of two-photon-photoelectron spectra at a jellium-vacuum interface}, year = {2005}, abstract = {In this paper we report on time dependent configuration interaction singles (TD-CIS) calculations aimed at simulating two-photon-photoelectron emission (2PPE) spectra of metal films, the latter treated within a one-dimensional jellium model. The method is based on a many-electron approach in which electron-electron-scattering is approximately accounted for and no artificial lifetimes have to be assumed for excited electrons. This contrasts with one-electron models where lifetimes and "dissipation" have to be introduced. The driving force for the photoelectron ejection in 2PPE experiments is the electric field of two laser pulses that are generally separated by a delay time, Delta t. To compute energy- and time-resolved 2PPE signals P(E, Delta t), a new scheme based on the time-energy method is proposed to analyze electronic wave packets in asymptotic regions of the potential}, language = {en} } @article{HuberKlamroth2011, author = {Huber, Christian and Klamroth, Tillmann}, title = {Explicitly time-dependent coupled cluster singles doubles calculations of laser-driven many-electron dynamics}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {134}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, number = {5}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.3530807}, pages = {8}, year = {2011}, abstract = {We report explicitly time-dependent coupled cluster singles doubles (TD-CCSD) calculations, which simulate the laser-driven correlated many-electron dynamics in molecular systems. Small molecules, i.e., HF, H(2)O, NH(3), and CH(4), are treated mostly with polarized valence double zeta basis sets. We determine the coupled cluster ground states by imaginary time propagation for these molecules. Excited state energies are obtained from the Fourier transform of the time-dependent dipole moment after an ultrashort, broadband laser excitation. The time-dependent expectation values are calculated from the complex cluster amplitudes using the corresponding configuration interaction singles doubles wave functions. Also resonant laser excitations of these excited states are simulated, in order to explore the limits for the numerical stability of our current TD-CCSD implementation, which uses time-independent molecular orbitals to form excited configurations.}, language = {en} } @article{Klamroth2006, author = {Klamroth, Tillmann}, title = {Optimal control of ultrafast laser driven many-electron dynamics in a polyatomic molecule: N-methyl-6-quinolone}, issn = {0021-9606}, doi = {10.1063/1.2185633}, year = {2006}, abstract = {We report time-dependent configuration interaction singles calculations for the ultrafast laser driven many- electron dynamics in a polyatomic molecule, N-methyl-6-quinolone. We employ optimal control theory to achieve a nearly state-selective excitation from the S-0 to the S-1 state, on a time scale of a few (approximate to 6) femtoseconds. The optimal control scheme is shown to correct for effects opposing a state-selective transition, such as multiphoton transitions and other, nonlinear phenomena, which are induced by the ultrashort and intense laser fields. In contrast, simple two-level pi pulses are not effective in state-selective excitations when very short pulses are used. Also, the dependence of multiphoton and nonlinear effects on the number of states included in the dynamical simulations is investigated.}, language = {en} } @phdthesis{Klamroth2006, author = {Klamroth, Tillmann}, title = {Quantum mechanical simulations for correlated many-electron dynamics and electron induced processes at surfaces}, address = {Potsdam}, pages = {206 S. : graph. Darst.}, year = {2006}, language = {en} } @article{Klamroth2003, author = {Klamroth, Tillmann}, title = {Laser-driven electron transfer through metal-insulator-metal contacts : time-dependent configuration interaction singles calculations for a jellium model}, issn = {1098-0121}, year = {2003}, abstract = {In this paper we report time-dependent configuration interaction singles calculations modeling the laser- induced current through a metal-insulator-metal (MIM) contact. We compare our results to recent experiments [D. Diesing, M. Merschdorf, A. Thon, and W. Pfeiffer, Appl. Phys. B (to be published)]. We use two jellium slabs separated by a vacuum region in a one-dimensional model to describe the MIM contact. The contact is coupled to ultrashort (fs) laser pulses by the semiclassical dipole approximation. We discuss simulated two-pulse correlation spectra in comparison to experimental results}, language = {en} } @article{KlamrothKronerSaalfrank2005, author = {Klamroth, Tillmann and Kroner, Dominic and Saalfrank, Peter}, title = {Laser-driven coupled electron-nuclear dynamics : Quantum mechanical simulation of molecular photodesorption from metal films}, issn = {1098-0121}, year = {2005}, abstract = {In this paper we report dynamical simulations of laser-driven, coupled nuclear-electron dynamics for a molecule- surface system. Specifically, the laser desorption of a small molecule (NO) from a metal slab (Pt) in the so-called DIET limit (Desorption Induced by Electronic Transitions), is studied. The excitation of the metal electrons by a laser pulse followed by the formation of a negative ion resonance, its subsequent decay, and the simultaneous desorption of the molecule are all treated within a single quantum mechanical model. This model is based on an earlier theory of Harris and others [S. M. Harris, S. Holloway, and G. R. Darling, J. Chem. Phys. 102, 8235 (1995)], according to which a nuclear degree of freedom is coupled to an electronic one, both propagated on a single non-Born-Oppenheimer potential energy surface. The goals of the present contribution are (i) to make a conceptual connection of this model to the frequently adopted nonadiabatic "multi-state" models of photodesorption, (ii) to understand details of the desorption mechanism, (iii) to explicitly account for the laser pulse, and (iv) to study the photodesorption as a function of the thickness of the metal film, and the laser parameters. As an important methodological aspect we also present a highly efficient numerical scheme to propagate the wave packet in a problem-adapted diabatic basis}, language = {en} } @article{KlamrothNest2009, author = {Klamroth, Tillmann and Nest, Mathias}, title = {Ultrafast electronic excitations of small sodium clusters and the onset of electron thermalization}, issn = {1463-9076}, doi = {10.1039/B813619j}, year = {2009}, abstract = {In this paper we report simulations of the ultrafast laser excitation and relaxation of the correlated valence electrons of a Na-8 cluster. The aim is twofold: first, while the total energy stays constant when the exciting laser pulse is over, we observe that the entropy computed from the reduced one electron density matrix rises on a much longer time scale. We discuss whether this can be understood as the onset of the thermalization of a finite system. Second, we describe this process with eight different methods of wavefunction-based electronic structure theory, which have been adapted for an explicitly time-dependent description. Their respective advantages and limitations for the simulation of the excitation and subsequent relaxation are explained.}, language = {en} } @article{KlinkuschKlamroth2013, author = {Klinkusch, Stefan and Klamroth, Tillmann}, title = {Simulations of pump-probe exitations of electronic wave packets for a large qusi-rigid molecular system by means of an extension to the time-dependent configuration interaction singles method}, series = {Journal of theoretical and computational chemistry}, volume = {12}, journal = {Journal of theoretical and computational chemistry}, number = {3}, publisher = {World Scientific}, address = {Singapore}, issn = {0219-6336}, doi = {10.1142/S0219633613500053}, pages = {17}, year = {2013}, abstract = {In this paper, we report simulations of laser-driven many-electron dynamics by means of the time-dependent configuration interaction singles (TD-CIS) approach. Photoionization is included by a heuristic model within calculations employing standard Gaussian basis sets. Benzo[g]-N-methyl-quinolinium-7-hydroxylate (BMQ7H) serves as a test system to generate predefined wave packets, i.e. a superposition between the ground and fifth excited state, in a large molecule. For this molecule, these two states have a very similar geometry, which enables us to use the fixed nuclei approximation. Furthermore, this geometric stability would also prevent a dephasing of the electron wave packet due to nuclear dynamics in an experimental realization of our simulations. We also simulate the possible detection of such a wave packet by ultra short probe laser pulses, i.e. pump-probe spectra.}, language = {en} } @article{KlinkuschKlamrothSaalfrank2009, author = {Klinkusch, Stefan and Klamroth, Tillmann and Saalfrank, Peter}, title = {Long-range intermolecular charge transfer induced by laser pulses : an explicitly time-dependent configuration interaction approach}, issn = {1463-9076}, doi = {10.1039/B817873a}, year = {2009}, abstract = {In this paper, we report simulations of laser-driven many-electron dynamics by means of the time-dependent configuration interaction singles (TD-CIS) approach. The method is capable of describing explicitly time-dependent phenomena beyond perturbation theory and is systematically improvable. In contrast to most time-dependent density functional methods it also allows us to treat long-range charge-transfer states properly. As an example, the laser-pulse induced charge transfer between a donor (ethylene) and an acceptor molecule (tetracyanoethylene, TCNE) is studied by means of TD-CIS. Also, larger aggregates consisting of several donors and/or acceptors are considered. It is shown that the charge distribution and hence the dipole moments of the systems under study are switchable by (a series of) laser pulses which induce selective, state-to-state electronic transitions.}, language = {en} } @article{KlinkuschSaalfrankKlamroth2009, author = {Klinkusch, Stefan and Saalfrank, Peter and Klamroth, Tillmann}, title = {Laser-induced electron dynamics including photoionization : a heuristic model within time-dependent configuration interaction theory}, issn = {0021-9606}, doi = {10.1063/1.3218847}, year = {2009}, abstract = {We report simulations of laser-pulse driven many-electron dynamics by means of a simple, heuristic extension of the time-dependent configuration interaction singles (TD-CIS) approach. The extension allows for the treatment of ionizing states as nonstationary states with a finite, energy-dependent lifetime to account for above-threshold ionization losses in laser-driven many-electron dynamics. The extended TD-CIS method is applied to the following specific examples: (i) state-to-state transitions in the LiCN molecule which correspond to intramolecular charge transfer, (ii) creation of electronic wave packets in LiCN including wave packet analysis by pump-probe spectroscopy, and, finally, (iii) the effect of ionization on the dynamic polarizability of H-2 when calculated nonperturbatively by TD-CIS.}, language = {en} } @article{KrausAschenbrennerKlamrothetal.2009, author = {Kraus, Florian and Aschenbrenner, J{\"u}rgen C. and Klamroth, Tillmann and Korber, Nikolaus}, title = {Hydrogen polyphosphides P3H23- and P3H32- : synthesis and crystal structure of K3(P3H2)·2.3NH3, Rb3(P3H2)·NH3, [Rb(18-crown-6)]2(P3H3)·7.5NH3, and [Cs(18-crown-6)]2(P3H3)·7NH3}, issn = {0020-1669}, doi = {10.1021/Ic8014546}, year = {2009}, abstract = {The incongruous solvation of polyphosphides and phosphanes or the direct reduction of white phosphorus in liquid ammonia leads to the hydrogen polyphosphides catena-dihydrogen triphosphide, P3H23-, and catena-trihydrogen triphosphide, P3H32-, in the crystalline compounds K-3(P3H2)center dot 2.3NH(3) (1), Rb-3(P3H2)center dot NH3 (2), [Rb(18-crown-6)](2)(P3H3)center dot 7.5NH(3) (3), and [Cs(18-crown-6)](2)(P3H3)center dot 7NH(3) (4).}, language = {en} } @article{KrauseKlamrothSaalfrank2005, author = {Krause, Pascal and Klamroth, Tillmann and Saalfrank, Peter}, title = {Time-dependent configuration-interaction calculations of laser-pulse-driven many-electron dynamics : Controlled dipole switching in lithium cyanide}, issn = {0021-9606}, year = {2005}, abstract = {We report simulations of laser-driven many-electron dynamics by means of the time-dependent configuration interaction singles (doubles) approach. The method accounts for the correlation of ground and excited states, is capable of describing explicitly time-dependent, nonlinear phenomena, and is systematically improvable. Lithium cyanide serves as a molecular test system in which the charge distribution and hence the dipole moment are shown to be switchable, in a controlled fashion, by (a series of) laser pulses which induce selective, state-to-state electronic transitions. One focus of our time-dependent calculations is the question of how fast the transition from the ionic ground state to a specific excited state that is embedded in a multitude of other states can be made, without creating an electronic wave packet. (c) 2005 American Institute of Physics}, language = {en} } @article{KroenerSchimkaKlamroth2014, author = {Kroener, Dominik and Schimka, Selina and Klamroth, Tillmann}, title = {Laser control for coupled torsions in chiroptical switches: a combined quantum and classical dynamics approach}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {118}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {2}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/jp410342a}, pages = {1322 -- 1331}, year = {2014}, abstract = {We present a novel laser pulse control for the chiroptical switch 1-(2-cis-fluoroethenyl)-2-fluoro-3,5-dibromobenzene mounted on adamantane, where the latter imitates a linker group or part of a solid surface. This molecular device offers three switching states: a true achiral "off"-state and two chiral "on"-states of opposite handedness. Due to the alignment of its chiral axis along the surface normal several defined orientations of the switch have to be considered for an efficient stereocontrol strategy. In addition to these different initial conditions, coupled torsional degrees of freedom around the chiral axis make the quest for highly stereoselective laser pulses a challenge. The necessary flexibility in pulse accomplished by employing the iterative stochastic pulse optimization method we presented recently. Still, the complexity of the system dictates a combined treatment by fast molecular dynamics and computationally intensive quantum dynamics. Although quantum effects are found to be of importance, the pulses optimized within the classical treatment allow us to turn on the chirality of the switch, achieving high enantioselectivity in the quantum treatment for all orientations at the same time.}, language = {en} } @article{MaassUtechtStremlauetal.2017, author = {Maass, Friedrich and Utecht, Manuel Martin and Stremlau, Stephan and Gille, Marie and Schwarz, Jutta and Hecht, Stefan and Klamroth, Tillmann and Tegeder, Petra}, title = {Electronic structure changes during the on-surface synthesis of nitrogen-doped chevron-shaped graphene nanoribbons}, series = {Physical review : B, Condensed matter and materials physics}, volume = {96}, journal = {Physical review : B, Condensed matter and materials physics}, publisher = {American Physical Society}, address = {College Park}, issn = {2469-9950}, doi = {10.1103/PhysRevB.96.045434}, pages = {7}, year = {2017}, abstract = {Utilizing suitable precursor molecules, a thermally activated and surface-assisted synthesis results in the formation of defect-free graphene nanoribbons (GNRs), which exhibit electronic properties that are not present in extended graphene. Most importantly, they have a band gap in the order of a few electron volts, depending on the nanoribbon width. In this study, we investigate the electronic structure changes during the formation of GNRs, nitrogen-doped (singly and doubly N-doped) as well as non-N-doped chevron-shaped CGNRs on Au(111). Thus we determine the optical gaps of the precursor molecules, the intermediate nonaromatic polymers, and finally the aromatic GNRs, using high-resolution electron energy loss spectroscopy and density functional theory calculations. As expected, we find no influence of N-doping on the size of the optical gaps. The gap of the precursor molecules is around 4.5 eV. Polymerization leads to a reduction of the gap to a value of 3.2 eV due to elongation and thus enhanced delocalization. The CGNRs exhibit a band gap of 2.8 eV, thus the gap is further reduced in the nanoribbons, since they exhibit an extended delocalized pi-electron system.}, language = {en} } @article{MalicWeberRichteretal.2011, author = {Malic, E. and Weber, C. and Richter, M. and Atalla, V. and Klamroth, Tillmann and Saalfrank, Peter and Reich, Sebastian and Knorr, A.}, title = {Microscopic model of the optical absorption of carbon nanotubes functionalized with molecular spiropyran photoswitches}, series = {Physical review letters}, volume = {106}, journal = {Physical review letters}, number = {9}, publisher = {American Physical Society}, address = {College Park}, issn = {0031-9007}, doi = {10.1103/PhysRevLett.106.097401}, pages = {4}, year = {2011}, abstract = {The adsorption of molecules to the surface of carbon nanostructures opens a new field of hybrid systems with distinct and controllable properties. We present a microscopic study of the optical absorption in carbon nanotubes functionalized with molecular spiropyran photoswitches. The switching process induces a change in the dipole moment leading to a significant coupling to the charge carriers in the nanotube. As a result, the absorption spectra of functionalized tubes reveal a considerable redshift of transition energies depending on the switching state of the spiropyran molecule. Our results suggest that carbon nanotubes are excellent substrates for the optical readout of spiropyran-based molecular switches. The gained insights can be applied to other noncovalently functionalized one-dimensional nanostructures in an externally induced dipole field.}, language = {en} } @article{NacciFoelschZenichowskietal.2009, author = {Nacci, Christophe and Foelsch, Stefan and Zenichowski, Karl and Dokic, Jadranka and Klamroth, Tillmann and Saalfrank, Peter}, title = {Current versus temperature-induced switching in a single-molecule tunnel junction : 1,5 cyclooctadiene on Si(001)}, issn = {1530-6984}, doi = {10.1021/Nl901419g}, year = {2009}, abstract = {The biconformational switching of single cyclooctadiene molecules chemisorbed on a Si(001) surface was explored by quantum chemical and quantum dynamical calculations and low-temperature scanning tunneling microscopy experiments. The calculations rationalize the experimentally observed switching driven by inelastic electron tunneling (IET) at 5 K. At higher temperatures, they predict a controllable crossover behavior between IET-driven and thermally activated switching, which is fully confirmed by experiment.}, language = {en} } @article{NestKlamroth2005, author = {Nest, Mathias and Klamroth, Tillmann}, title = {Correlated many-electron dynamics : application to inelastic electron scattering at a metal film}, year = {2005}, abstract = {The multiconfiguration time-dependent Hartree-Fock and the time-dependent configuration interaction singles method are applied to the correlated many-electron dynamics of a one-dimensional jellium model system. We study the scattering of an initially free electron at a model film in the framework of both approaches. In particular, both methods are compared with regard to how they describe the underlying physical processes, namely inelastic electron scattering, inverse photoemission, and electron impact ionization}, language = {en} } @article{NestKlamrothSaalfrank2005, author = {Nest, Mathias and Klamroth, Tillmann and Saalfrank, Peter}, title = {The multiconfiguration time-dependent Hartree-Fock method for quantum chemical calculations}, issn = {0021-9606}, year = {2005}, abstract = {We apply the multiconfiguration time-dependent Hartree-Fock method to electronic structure calculations and show that quantum chemical information can be obtained with this explicitly time-dependent approach. Different equations of motion are discussed, as well as the numerical cost. The two-electron integrals are calculated using a natural potential expansion, of which we describe the convergence behavior in detail}, language = {en} } @article{NestLudwigUlusoyetal.2013, author = {Nest, Mathias and Ludwig, M. and Ulusoy, I. and Klamroth, Tillmann and Saalfrank, Peter}, title = {Electron correlation dynamics in atoms and molecules}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {138}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, number = {16}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.4801867}, pages = {6}, year = {2013}, abstract = {In this paper, we present quantum dynamical calculations on electron correlation dynamics in atoms and molecules using explicitly time-dependent ab initio configuration interaction theory. The goals are (i) to show that in which cases it is possible to switch off the electronic correlation by ultrashort laser pulses, and (ii) to understand the temporal evolution and the time scale on which it reappears. We characterize the appearance of correlation through electron-electron scattering when starting from an uncorrelated state, and we identify pathways for the preparation of a Hartree-Fock state from the correlated, true ground state. Exemplary results for noble gases, alkaline earth elements, and selected molecules are provided. For Mg we show that the uncorrelated state can be prepared using a shaped ultrashort laser pulse.}, language = {en} } @article{ParamonovKlamrothLuetal.2018, author = {Paramonov, Guennaddi K. and Klamroth, Tillmann and Lu, H. Z. and Bandrauk, Andre D.}, title = {Quantum dynamics, isotope effects, and power spectra of H-2(+) and HD+ excited to the continuum by strong one-cycle laser pulses: Three-dimensional non-Born-Oppenheimer simulations}, series = {Physical review : A, Atomic, molecular, and optical physics}, volume = {98}, journal = {Physical review : A, Atomic, molecular, and optical physics}, number = {6}, publisher = {American Physical Society}, address = {College Park}, issn = {2469-9926}, doi = {10.1103/PhysRevA.98.063431}, pages = {16}, year = {2018}, abstract = {Non-Born-Oppenheimer quantum dynamics of H-2(+) and HD+ excited by single one-cycle laser pulses linearly polarized along the molecular (z) axis have been studied within a three-dimensional model, including the internuclear distance R and electron coordinates z and rho, by means of the numerical solution of the time-dependent Schrodinger equation on the timescale of about 200 fs. Laser carrier frequencies corresponding to the wavelengths of lambda(l) = 400 and 50 nm have been used and the amplitudes of the pulses have been chosen such that the energies of H-2(+) and HD+ are above the dissociation threshold after the ends of the laser pulses. It is shown that excitation of H-2(+) and HD+ above the dissociation threshold is accompanied by formation of vibrationally "hot" and "cold" ensembles of molecules. Dissociation of vibrationally "hot" molecules does not prevent the appearance of post-laser-pulse electronic oscillations, parallel z oscillations, and transversal rho oscillations. Moreover, dissociation of "hot" molecules does not influence characteristic frequencies of electronic z and rho oscillations. The main difference between the laser-induced quantum dynamics of homonuclear H-2(+) and its heteronuclear isotope HD+ is that fast post-laser-pulse electronic z oscillations in H-2(+) are regularly shaped with the period of tau(shp) approximate to 30 fs corresponding to nuclear oscillations in H-2(+), while electronic z oscillations in HD+ arise as "echo pulses" of its initial excitation and appear with the period of tau(echo) approximate to 80 fs corresponding to nuclear motion in HD+. Accordingly, corresponding power spectra of nuclear motion contain strong low-frequency harmonics at omega(shp) = 2 pi/tau(shp) in H2(+) and omega(echo) = 2 pi/tau(echo) in HD+. Power spectra related to both electronic and nuclear motion have been calculated in the acceleration form. Both higher- and lower-order harmonics are generated at the laser wavelength lambda(l) = 400 nm, while only lower-order harmonics are well pronounced at lambda(l) = 50 nm. It is also shown that a rationalized harmonic order, defined in terms of the frequency of the laser-induced electronic z oscillations, agrees with the concept of inversion symmetry for electronic motion in diatomic molecules.}, language = {en} } @incollection{SaalfrankBedurkeHeideetal.2020, author = {Saalfrank, Peter and Bedurke, Florian and Heide, Chiara and Klamroth, Tillmann and Klinkusch, Stefan and Krause, Pascal and Nest, Mathias and Tremblay, Jean Christophe}, title = {Molecular attochemistry: correlated electron dynamics driven by light}, series = {Advances in quantum chemistry}, volume = {81}, booktitle = {Advances in quantum chemistry}, editor = {Ruud, Kenneth and Br{\"a}ndas, Erkki J.}, publisher = {Elsevier}, address = {Amsterdam [u.a.]}, isbn = {978-0-12-819757-8}, issn = {0065-3276}, doi = {10.1016/bs.aiq.2020.03.001}, pages = {15 -- 50}, year = {2020}, abstract = {Modern laser technology and ultrafast spectroscopies have pushed the timescales for detecting and manipulating dynamical processes in molecules from the picosecond over femtosecond domains, to the attosecond regime (1 as = 10(-18) s). This way, real-time dynamics of electrons after their photoexcitation can be probed and manipulated. In particular, experiments are moving more and more from atomic and solid state systems to molecules, opening the fields of "molecular electron dynamics" and "attosecond chemistry." Also on the theory side, powerful quantum dynamical tools have been developed to rationalize experiments on ultrafast electron dynamics in molecular species.
In this contribution, we concentrate on theoretical aspects of ultrafast electron dynamics in molecules, mostly driven by lasers. The dynamics will be described with the help of wavefunction-based ab initio methods such as time-dependent configuration interaction (TD-CI) or the multiconfigurational time-dependent Hartree-Fock (MCTDHF) methods. Besides a survey of the methods and their extensions toward, e.g., treatment of ionization, laser pulse optimization, and open quantum systems, two specific examples of applications will be considered: The creation and/or dynamical fate of electronic wavepackets, and the nonlinear optical response to laser pulse excitation in molecules by high harmonic generation (HHG).}, language = {en} } @article{SaalfrankKlamrothHuberetal.2005, author = {Saalfrank, Peter and Klamroth, Tillmann and Huber, C. and Krause, Pascal}, title = {Laser-driven electron dynamics at interfaces}, issn = {0021-2148}, year = {2005}, abstract = {In this paper we present time-dependent, quantum-dynamical simulations of photoinduced processes at solid surfaces involving nonadiabatic transitions of electrons to and from short-lived intermediate excited states. In particular, two-photon photoemission (2PPE) spectra of naked metal surfaces and free-standing metal films are considered. One major problem in both cases is the presence of electron-electron scattering, which is treated here in various ways. The first way is to adopt an open-system density matrix approach, in which a single electron is weakly coupled to a "bath" of other electrons. The second approach is based on a many-electron Schrodinger equation, which is solved with the help of a time-dependent configuration interactions singles (TD-CIS) method}, language = {en} } @article{SaalfrankNestAndrianovetal.2006, author = {Saalfrank, Peter and Nest, Mathias and Andrianov, Igor V. and Klamroth, Tillmann and Kroner, Dominic and Beyvers, Stephanie}, title = {Quantum dynamics of laser-induced desorption from metal and semiconductor surfaces, and related phenomena}, volume = {18}, number = {30}, publisher = {IOP Publ.}, address = {Bristol}, issn = {1361-648X}, doi = {10.1088/0953-8984/18/30/S05}, pages = {S1425 -- S1459}, year = {2006}, abstract = {Recent progress towards a quantum theory of laser-induced desorption and related phenomena is reviewed, for specific examples. These comprise the photodesorption of NO from Pt(111), the scanning tunnelling microscope and laser- induced desorption and switching of H at Si(100), and the electron stimulated desorption and dissociation of CO at Ru(0001). The theoretical methods used for nuclear dynamics range from open-system density matrix theory over nonadiabatically coupled multi-state models to electron-nuclear wavepackets. Also, aspects of time-dependent spectroscopy to probe ultrafast nonadiabatic processes at surfaces will be considered for the example of two-photon photoemission of solvated electrons in ice layers on Cu(111)}, language = {en} } @article{SchwarzeDoscheFlehretal.2010, author = {Schwarze, Thomas and Dosche, Carsten and Flehr, Roman and Klamroth, Tillmann and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Saalfrank, Peter and Cleve, Ernst and Buschmann, Hans-J{\"u}rgen and Holdt, Hans-J{\"u}rgen}, title = {Combination of a CT modulated PET and an intramolecular excimer formation to quantify PdCl2 by large fluorescence enhancement}, issn = {1359-7345}, doi = {10.1039/B919973j}, year = {2010}, abstract = {The [6.6](9,10)anthracenophane 1 (Scheme 1) is a selective fluoroionophore for the detection of PdCl2 with a large fluorescence enhancement factor (I/I-0 > 250).}, language = {en} } @article{SchwarzeDoscheFlehretal.2010, author = {Schwarze, Thomas and Dosche, Carsten and Flehr, Roman and Klamroth, Tillmann and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Saalfrank, Peter and Cleve, Ernst and Buschmann, Hans-J{\"u}rgen and Holdt, Hans-J{\"u}rgen}, title = {Combination of a CT modulated PET and an intramolecular excimer formation to quantify PdCl2 by large fluorescence enhancement}, issn = {1359-7345}, year = {2010}, language = {en} } @article{SchwarzeKellingMuelleretal.2012, author = {Schwarze, Thomas and Kelling, Alexandra and M{\"u}ller, Holger and Trautmann, Michael and Klamroth, Tillmann and Baumann, Otto and Strauch, Peter and Holdt, Hans-J{\"u}rgen}, title = {N-2-Pyridinylmethyl-N '-arylmethyl-diaminomaleonitriles: New Highly Selective Chromogenic Chemodosimeters for Copper(II)}, series = {Chemistry - a European journal}, volume = {18}, journal = {Chemistry - a European journal}, number = {34}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201201731}, pages = {10506 -- 10510}, year = {2012}, language = {en} } @article{SchwarzeMicklerDoscheetal.2010, author = {Schwarze, Thomas and Mickler, Wulfhard and Dosche, Carsten and Flehr, Roman and Klamroth, Tillmann and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Saalfrank, Peter and Holdt, Hans-J{\"u}rgen}, title = {Systematic investigation of photoinduced electron transfer controlled by internal charge transfer and its consequences for selective PdCl2 coordination}, issn = {0947-6539}, doi = {10.1002/chem.200902281}, year = {2010}, abstract = {Fluoroionophores of fluorophore-spacer-receptor format were prepared for detection of PdCl2 by fluorescence enhancement. The fluorophore probes 1-13 consist of a fluorophore group, in alkyl spacer and a dithiomaleonitrile PdCl2 receptor. First, varying the length of the alkylene spacer (compounds 1-3) revealed, dominant through-space pathway for oxidative photoinduced electron transfer (PET) in CH2-bridged dithiomaleonitrile fluoroionophores. Second. fluorescent probes 4-9 containing two anthracene or pyrene fragments connected through CH2 bridges to the dithiomaleonitrile unit were synthesized. Modulation of the oxidation potential (E-Ox) through electron-withdrawing or -donating groups on the anthracene moiety regulates file thermodynamic driving force for oxidative PET (Delta G(PET)) in bis(anthrylmethylthio)maleonitriles and therefore the fluorescence quantum yields (Phi(f)), too. The new concept was confirmed and transferred to pyrenyl ligands, and fluorescence enhancements (FE) greater than 3.2 in the presence of PdCl2 were achieved by 7 and 8 (FE=5.4 and 5.2). Finally, for comparison, monofluorophore ligands 10-13 were synthesized.}, language = {en} } @article{SchwarzeMicklerDoscheetal.2010, author = {Schwarze, Thomas and Mickler, Wulfhard and Dosche, Carsten and Flehr, Roman and Klamroth, Tillmann and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Saalfrank, Peter and Holdt, Hans-J{\"u}rgen}, title = {Systematic investigation of photoinduced electron transfer controlled by internal charge transfer and its consequences for selective PdCl2 coordination}, issn = {0947-6539}, year = {2010}, abstract = {Fluoroionophores of fluorophore-spacer-receptor format were prepared for detection of PdCl2 by fluorescence enhancement. The fluorescent probes 1-13 consist of a fluorophore group, an alkyl spacer and a dithiomaleonitrile PdCl2 receptor. First, varying the length of the alkylene spacer (compounds 1-3) revealed a dominant through-space pathway for oxidative photoinduced electron transfer (PET) in CH2-bridged dithiomaleonitrile fluoroionophores. Second, fluorescent probes 4-9 containing two anthracene or pyrene fragments connected through CH2 bridges to the dithiomaleonitrile unit were synthesized. Modulation of the oxidation potential (EOx) through electron-withdrawing or -donating groups on the anthracene moiety regulates the thermodynamic driving force for oxidative PET (GPET) in bis(anthrylmethylthio)maleonitriles and therefore the fluorescence quantum yields (f), too. The new concept was confirmed and transferred to pyrenyl ligands, and fluorescence enhancements (FE) greater than 3.2 in the presence of PdCl2 were achieved by 7 and 8 (FE=5.4 and 5.2). Finally, for comparison, monofluorophore ligands 10-13 were synthesized.}, language = {en} } @article{SchwarzeMuellerDoscheetal.2007, author = {Schwarze, Thomas and Mueller, Holger and Dosche, Carsten and Klamroth, Tillmann and Mickler, Wulfhard and Kelling, Alexandra}, title = {Luminescence detection of open-shell transition-metal ions by photoinduced electron transfer controlled by internal charge transfer of a receptor}, doi = {10.1002/anie.200603992}, year = {2007}, language = {en} } @article{SchoenbornSaalfrankKlamroth2016, author = {Sch{\"o}nborn, Jan Boyke and Saalfrank, Peter and Klamroth, Tillmann}, title = {Controlling the high frequency response of H-2 by ultra-short tailored laser pulses: A time-dependent configuration interaction study}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {144}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.4940316}, pages = {9}, year = {2016}, abstract = {We combine the stochastic pulse optimization (SPO) scheme with the time-dependent configuration interaction singles method in order to control the high frequency response of a simple molecular model system to a tailored femtosecond laser pulse. For this purpose, we use H-2 treated in the fixed nuclei approximation. The SPO scheme, as similar genetic algorithms, is especially suited to control highly non-linear processes, which we consider here in the context of high harmonic generation. Here, we will demonstrate that SPO can be used to realize a "non-harmonic" response of H2 to a laser pulse. Specifically, we will show how adding low intensity side frequencies to the dominant carrier frequency of the laser pulse and stochastically optimizing their contribution can create a high-frequency spectral signal of significant intensity, not harmonic to the carrier frequency. At the same time, it is possible to suppress the harmonic signals in the same spectral region, although the carrier frequency is kept dominant during the optimization. (C) 2016 AIP Publishing LLC.}, language = {en} } @article{ThielKlamrothStrauchetal.2011, author = {Thiel, Kerstin and Klamroth, Tillmann and Strauch, Peter and Taubert, Andreas}, title = {On the interaction of ascorbic acid and the tetrachlorocuprate ion [CuCl4](2-) in CuCl nanoplatelet formation from an ionic liquid precursor (ILP)}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {13}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, number = {30}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c1cp20648f}, pages = {13537 -- 13543}, year = {2011}, abstract = {The formation of CuCl nanoplatelets from the ionic liquid precursor (ILP) butylpyridinium tetrachlorocuprate [C4Py](2)[CuCl4] using ascorbic acid as a reducing agent was investigated. In particular, electron paramagnetic resonance (EPR) spectroscopy was used to evaluate the interaction between ascorbic acid and the Cu(II) ion before reduction to Cu(I). EPR spectroscopy suggests that the [CuCl4](2-) ion in the neat IL is a distorted tetrahedron, consistent with DFT calculations. Addition of ascorbic acid leads to the removal of one chloride from the [CuCl4](2-) anion, as shown by DFT and the loss of symmetry by EPR. DFT furthermore suggests that the most stable adduct is formed when only one hydroxyl group of the ascorbic acid coordinates to the Cu(II) ion.}, language = {en} } @article{TremblayKlinkuschKlamrothetal.2011, author = {Tremblay, Jean Christophe and Klinkusch, Stefan and Klamroth, Tillmann and Saalfrank, Peter}, title = {Dissipative many-electron dynamics of ionizing systems}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {134}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, number = {4}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.3532410}, pages = {10}, year = {2011}, abstract = {In this paper, we perform many-electron dynamics using the time-dependent configuration-interaction method in its reduced density matrix formulation (rho-TDCI). Dissipation is treated implicitly using the Lindblad formalism. To include the effect of ionization on the state-resolved dynamics, we extend a recently introduced heuristic model for ionizing states to the rho-TDCI method, which leads to a reduced density matrix evolution that is not norm-preserving. We apply the new method to the laser-driven excitation of H(2) in a strongly dissipative environment, for which the state-resolve lifetimes are tuned to a few femtoseconds, typical for dynamics of adsorbate at metallic surfaces. Further testing is made on the laser-induced intramolecular charge transfer in a quinone derivative as a model for a molecular switch. A modified scheme to treat ionizing states is proposed to reduce the computational burden associated with the density matrix propagation, and it is thoroughly tested and compared to the results obtained with the former model. The new approach scales favorably (similar to N(2)) with the number of configurations N used to represent the reduced density matrix in the rho-TDCI method, as compared to a N(3) scaling for the model in its original form.}, language = {en} }