Publications

2017

  • [DOI] M. Richter and B. P. Fingerhut, “Coarse-grained representation of the quasi adiabatic propagator path integral for the treatment of non-Markovian long-time bath memory,” J. Chem. Phys., vol. 146, iss. 21, p. 214101, 2017.
    [Bibtex]
    @article{Richter_JCP_2017,
    author = {Martin Richter and Benjamin P. Fingerhut},
    title = {Coarse-grained representation of the quasi adiabatic propagator path integral for the treatment of non-Markovian long-time bath memory},
    journal = {J. Chem. Phys.},
    volume = {146},
    number = {21},
    pages = {214101},
    year = {2017},
    doi = {10.1063/1.4984075},
    URL = {http://dx.doi.org/10.1063/1.4984075},
    eprint = {http://dx.doi.org/10.1063/1.4984075}
    }
  • [DOI] Y. Liu, B. Guchhait, T. Siebert, B. P. Fingerhut, and T. Elsaesser, “Molecular couplings and energy exchange between DNA and water mapped by femtosecond infrared spectroscopy of backbone vibrations,” Struct. Dynamics, vol. 4, iss. 4, p. 44015, 2017.
    [Bibtex]
    @article{Liu_StructDyn_2017,
    author = {Yingliang Liu and Biswajit Guchhait and Torsten Siebert and Benjamin P. Fingerhut and Thomas Elsaesser},
    title = {Molecular couplings and energy exchange between DNA and water mapped by femtosecond infrared spectroscopy of backbone vibrations},
    journal = {Struct. Dynamics},
    volume = {4},
    number = {4},
    pages = {044015},
    year = {2017},
    doi = {10.1063/1.4980075},
    URL = {http://dx.doi.org/10.1063/1.4980075},
    eprint = {http://dx.doi.org/10.1063/1.4980075}
    }
  • [DOI] E. Riedle, M. K. Roos, S. Thallmair, C. F. Sailer, N. Krebs, B. P. Fingerhut, and R. de Vivie-Riedle, “Ultrafast photochemistry with two product channels: Wavepacket motion through two distinct conical intersections,” Chem. Phys. Lett., p. in press, 2017.
    [Bibtex]
    @article{Riedle_CPL_2017,
    title = "Ultrafast photochemistry with two product channels: Wavepacket motion through two distinct conical intersections ",
    journal = "Chem. Phys. Lett.",
    volume = "",
    number = "",
    pages = "in press",
    year = "2017",
    note = "",
    issn = "0009-2614",
    doi = "https://doi.org/10.1016/j.cplett.2017.02.086",
    url = "http://www.sciencedirect.com/science/article/pii/S000926141730204X",
    author = "Eberhard Riedle and Matthias K. Roos and Sebastian Thallmair and Christian F. Sailer and Nils Krebs and Benjamin P. Fingerhut and Regina de Vivie-Riedle",
    keywords = "Femtosecond photodissociation",
    keywords = "Conical intersection",
    keywords = "Competing channels ",
    abstract = "Abstract Light induced bond cleavage is an ubiquitous process in large molecules, yet its quantum nature is not fully understood. We present a comprehensive description of the ultrafast light induced \{CCl\} bond cleavage in diarylmethyl chlorides combining femtosecond transient absorption measurements with ab initio calculations. We observe a delayed appearance of radicals (80 fs) and cations (125 fs). The excited state wavepacket moves initially toward two conical intersections and the passing through these intersections determines the partitioning into the differing product channels. Different locations of the conical intersections explain the observed delay times. "
    }

2016

  • [DOI] B. P. Fingerhut, R. Costard, and T. Elsaesser, “Predominance of short range Coulomb forces in phosphate-water interactions—a theoretical analysis,” J.Chem. Phys., vol. 145, iss. 11, p. 115101, 2016.
    [Bibtex]
    @article{Fingerhut_JCP_2016,
    author = {Benjamin P. Fingerhut and Rene Costard and Thomas Elsaesser},
    title = {Predominance of short range Coulomb forces in phosphate-water interactions—a theoretical analysis},
    journal = {J.Chem. Phys.},
    volume = {145},
    number = {11},
    pages = {115101},
    year = {2016},
    doi = {10.1063/1.4962755},
    URL = {http://dx.doi.org/10.1063/1.4962755},
    eprint = {http://dx.doi.org/10.1063/1.4962755}
    }
  • [DOI] T. Siebert, B. Guchhait, Y. Liu, B. P. Fingerhut, and T. Elsaesser, “Range, Magnitude, and Ultrafast Dynamics of Electric Fields at the Hydrated DNA Surface,” J. Phys. Chem. Lett., vol. 7, iss. 16, pp. 3131-3136, 2016.
    [Bibtex]
    @article{Siebert_JPCLett_2016,
    author = {Siebert, Torsten and Guchhait, Biswajit and Liu, Yingliang and Fingerhut, Benjamin P. and Elsaesser, Thomas},
    title = {Range, Magnitude, and Ultrafast Dynamics of Electric Fields at the Hydrated DNA Surface},
    journal = {J. Phys. Chem. Lett.},
    volume = {7},
    number = {16},
    pages = {3131-3136},
    year = {2016},
    doi = {10.1021/acs.jpclett.6b01369},
    note ={PMID: 27468144},
    URL = {
    http://dx.doi.org/10.1021/acs.jpclett.6b01369
    },
    eprint = {
    http://dx.doi.org/10.1021/acs.jpclett.6b01369
    }
    ,
    abstract = { Range and magnitude of electric fields at biomolecular interfaces and their fluctuations in a time window down to the subpicosecond regime have remained controversial, calling for electric-field mapping in space and time. Here, we trace fluctuating electric fields at the surface of native salmon DNA via their interactions with backbone vibrations in a wide range of hydration levels by building the water shell layer by layer. Femtosecond two-dimensional infrared spectroscopy and ab initio based theory establish water molecules in the first two layers as the predominant source of interfacial electric fields, which fluctuate on a 300 fs time scale with an amplitude of 25 MV/cm due to thermally excited water motions. The observed subnanometer range of these electric interactions is decisive for biochemical structure and function. }
    }
  • [DOI] F. Dahms, R. Costard, E. Pines, B. P. Fingerhut, E. T. J. Nibbering, and T. Elsaesser, “The Hydrated Excess Proton in the Zundel Cation H5O2+: The Role of Ultrafast Solvent Fluctuations,” Angew. Chem. Int. Ed., vol. 55, iss. 36, pp. 10600-10605, 2016.
    [Bibtex]
    @article {Dahms_AngewChem_2016,
    author = {Dahms, Fabian and Costard, Rene and Pines, Ehud and Fingerhut, Benjamin P. and Nibbering, Erik T. J. and Elsaesser, Thomas},
    title = {The Hydrated Excess Proton in the Zundel Cation H5O2+: The Role of Ultrafast Solvent Fluctuations},
    journal = {Angew. Chem. Int. Ed.},
    volume = {55},
    number = {36},
    issn = {1521-3773},
    url = {http://dx.doi.org/10.1002/anie.201602523},
    doi = {10.1002/anie.201602523},
    pages = {10600--10605},
    keywords = {femtochemistry, hydrated protons, solvation dynamics, Zundel cation, Zundel continuum},
    year = {2016},
    abstract = {The nature of the excess proton in liquid water has remained elusive after decades of extensive research. In view of ultrafast structural fluctuations of bulk water scrambling the structural motifs of excess protons in water, we selectively probe prototypical protonated water solvates in acetonitrile on the femtosecond time scale. Focusing on the Zundel cation H5O2+ prepared in room-temperature acetonitrile, we unravel the distinct character of its vibrational absorption continuum and separate it from OH stretching and bending excitations in transient pump-probe spectra. The infrared absorption continuum originates from a strong ultrafast frequency modulation of the H+ transfer vibration and its combination and overtones. Vibrational lifetimes of H5O2+ are found to be in the sub-100 fs range, much shorter than those of unprotonated water. Theoretical results support a picture of proton hydration where fluctuating electrical interactions with the solvent and stochastic thermal excitations of low-frequency modes continuously modify the proton binding site while affecting its motions.},
    }
  • [DOI] M. Richter and B. P. Fingerhut, “Simulation of Multi-Dimensional Signals in the Optical Domain: Quantum-Classical Feedback in Nonlinear Exciton Propagation,” J. Chem. Theory Comput., vol. 12, iss. 7, p. 3284–3294, 2016.
    [Bibtex]
    @article{doi:10.1021/acs.jctc.6b00371,
    author = {Martin Richter and Benjamin P. Fingerhut },
    title = {Simulation of Multi-Dimensional Signals in the Optical Domain: Quantum-Classical Feedback in Nonlinear Exciton Propagation},
    journal = {J. Chem. Theory Comput.},
    volume = {12},
    number = {7},
    pages = {3284–3294},
    year = {2016},
    doi = {10.1021/acs.jctc.6b00371},
    note ={PMID: 27248511},
    URL = {
    http://dx.doi.org/10.1021/acs.jctc.6b00371
    },
    eprint = {
    http://dx.doi.org/10.1021/acs.jctc.6b00371
    }
    ,
    abstract = { We present an algorithm for the simulation of nonlinear 2D spectra of molecular systems in the UV-Vis spectral region from atomistic molecular dynamics trajectories subject to non-adiabatic relaxation. We combine the nonlinear exciton propagation (NEP) protocol, that relies on a quasiparticle approach with the surface hopping methodology to account for quantum-classical feedback during the dynamics. Phenomena like dynamic Stokes shift due to nuclear relaxation, spectral diffusion and population transfer among electronic states are thus naturally included and benchmarked on a model of two electronic states coupled to a harmonic coordinate and a classical heatbath. The capabilities of the algorithm are further demonstrated for the bichromophore diphenylmethane that is described in a fully microscopic fashion including all 69 classical nuclear degrees of freedom. We demonstrate that simulated 2D signals are especially sensitive to the applied theoretical approximations (i.e. choice of active space in the CASSCF method) where population dynamics appears comparable. }
    }
  • [DOI] R. Costard, T. Tyborski, and B. Fingerhut, “Coherent Dynamics of Phosphate Ions in Bulk H2O,” in International Conference on Ultrafast Phenomena, 2016, p. UTh3B.7.
    [Bibtex]
    @inproceedings{Costard:16,
    author = {Rene Costard and Tobias Tyborski and Benjamin Fingerhut},
    booktitle = {International Conference on Ultrafast Phenomena},
    journal = {International Conference on Ultrafast Phenomena},
    keywords = {Spectroscopy, infrared; Spectroscopy, ultrafast; Ultrafast phenomena},
    pages = {UTh3B.7},
    publisher = {Optical Society of America},
    title = {Coherent Dynamics of Phosphate Ions in Bulk H2O},
    year = {2016},
    url = {http://www.osapublishing.org/abstract.cfm?URI=UP-2016-UTh3B.7},
    doi = {10.1364/UP.2016.UTh3B.7},
    abstract = {Phosphates as important biomolecular building blocks are studied by 2D-IR spectroscopy. Excitation with spectrally broad pulses generates a coherent superposition of phosphate stretching modes resulting in the observation of quantum beats in aqueous solution.},
    }
  • [DOI] F. Dahms, R. Costard, B. P. Fingerhut, E. Pines, E. T. J. Nibbering, and T. Elsaesser, “The Hydrated Excess Proton – Ultrafast Vibrational Dynamics of the Zundel Cation H5O2 $+$,” in International Conference on Ultrafast Phenomena, 2016, p. UTh4A.8.
    [Bibtex]
    @inproceedings{Dahms:16,
    author = {Fabian Dahms and Rene Costard and Benjamin P. Fingerhut and Ehud Pines and Erik T.J. Nibbering and Thomas Elsaesser},
    booktitle = {International Conference on Ultrafast Phenomena},
    journal = {International Conference on Ultrafast Phenomena},
    keywords = {Spectroscopy, condensed matter; Spectroscopy, infrared; Ultrafast spectroscopy},
    pages = {UTh4A.8},
    publisher = {Optical Society of America},
    title = {The Hydrated Excess Proton - Ultrafast Vibrational Dynamics of the Zundel Cation H5O2 $+$},
    year = {2016},
    url = {http://www.osapublishing.org/abstract.cfm?URI=UP-2016-UTh4A.8},
    doi = {10.1364/UP.2016.UTh4A.8},
    abstract = {Femtosecond infrared spectroscopy allows for separating the absorption continuum of hydrated protons in solution from OH stretching and bending excitations of H5O2 $+$. The extremely broad lineshape of the proton transfer vibration originates from solvent fluctuations.},
    }
  • [DOI] W. Hua, S. Oesterling, J. D. Biggs, Y. Zhang, H. Ando, R. de Vivie-Riedle, B. P. Fingerhut, and S. Mukamel, “Monitoring conical intersections in the ring opening of furan by attosecond stimulated X-ray Raman spectroscopy,” Struct. Dynamics, vol. 3, p. 23601, 2016.
    [Bibtex]
    @Article{Hua:2016,
    author ={Hua, Weijie and Oesterling, Sven and Biggs, Jason D. and Zhang, Yu and Ando, Hideo and de Vivie-Riedle, Regina and Fingerhut, Benjamin P. and Mukamel, Shaul},
    title ={Monitoring conical intersections in the ring opening of furan by attosecond stimulated X-ray Raman spectroscopy},
    year ={2016},
    volume ={3},
    pages ={023601},
    journal ={Struct. Dynamics},
    doi ={10.1063/1.4933007},
    url ={http://dx.doi.org/10.1063/1.4933007},
    abstract ={Attosecond X-ray pulses are short enough to capture snapshots of molecules under- going nonadiabatic electron and nuclear dynamics at conical intersections (CoIns). We show that a stimulated Raman probe induced by a combination of an attosecond and a femtosecond pulse has a unique temporal and spectral resolution for probing the nonadiabatic dynamics and detecting the ultrafast ($\approx$ 4.5 fs) passage through a CoIn. This is demonstrated by a multiconfigurational self-consistent-field (MCSCF) study of the dynamics and spectroscopy of the furan ring-opening reaction. Trajectories generated by surface hopping simulations were used to predict ASRS signals at reactant and product structures as well as representative snapshots along the conical intersection seam. The signals are highly sensitive to the changes in nonadiabatically coupled electronic structure and geometry.}
    }

2015

  • [DOI] R. Costard, T. Tyborski, and B. P. Fingerhut, “Anharmonicities and coherent vibrational dynamics of phosphate ions in bulk H2O,” Phys. Chem. Chem. Phys., vol. 17, pp. 29906-29917, 2015.
    [Bibtex]
    @Article{Costard_PCCP_C5CP04502A:2015,
    author ={Costard, Rene and Tyborski, Tobias and Fingerhut, Benjamin P.},
    title ={Anharmonicities and coherent vibrational dynamics of phosphate ions in bulk H2O},
    journal ={Phys. Chem. Chem. Phys.},
    year ={2015},
    volume ={17},
    pages ={29906-29917},
    publisher ={The Royal Society of Chemistry},
    doi ={10.1039/C5CP04502A},
    url ={http://dx.doi.org/10.1039/C5CP04502A},
    abstract ={Phosphates feature prominently in the energetics of metabolism and are important solvation sites of DNA and phospholipids. Here we investigate the ion H$_2$PO$_4^-$ in aqueous solution combining 2D IR spectroscopy of phosphate stretching vibrations in the range from 900-1300 cm$^{-1}$ with ab-initio calculations and hybrid quantum-classical molecular dynamics based simulations of the non-linear signal. While the line shapes of diagonal peaks reveal ultrafast frequency fluctuations on a sub-100 fs timescale caused by the fluctuating hydration shell{,} an analysis of the diagonal and cross-peak frequency positions allows for extracting inter-mode couplings and anharmonicities of 5-10 cm$^{-1}$. The excitation with spectrally broad pulses generates a coherent superposition of symmetric and asymmetric PO_2^- stretching modes resulting in the observation of a quantum beat in aqueous solution. We follow its time evolution through the time-dependent amplitude and shape of the cross peaks. The results provide a complete characterization of the H$_2$PO$_4^-$ vibrational Hamiltonian including fluctuations induced by the native water environment.}
    }
  • [DOI] A. Nenov, A. Giussani, B. P. Fingerhut, I. Rivalta, E. Dumont, S. Mukamel, and M. Garavelli, “Spectral lineshapes in nonlinear electronic spectroscopy,” Phys. Chem. Chem. Phys., vol. 17, pp. 30925-30936, 2015.
    [Bibtex]
    @Article{Nenov:2015,
    author ="Nenov, Artur and Giussani, Angelo and Fingerhut, Benjamin P. and Rivalta, Ivan and Dumont, Elise and Mukamel, Shaul and Garavelli, Marco",
    title ="Spectral lineshapes in nonlinear electronic spectroscopy",
    journal ="Phys. Chem. Chem. Phys.",
    year ="2015",
    volume = "17",
    pages ="30925-30936",
    publisher ="The Royal Society of Chemistry",
    doi ="10.1039/C5CP01167A",
    url ="http://dx.doi.org/10.1039/C5CP01167A",
    abstract ="We outline a computational approach for nonlinear electronic spectra{,} which accounts for the electronic energy fluctuations due to nuclear degrees of freedom and explicitly incorporates the fluctuations of higher excited states{,} induced by the dynamics in the photoactive state(s). The approach is based on mixed quantum-classical dynamics simulations. Tedious averaging over multiple trajectories is avoided by employing the linearly displaced Brownian harmonic oscillator to model the correlation functions. The present strategy couples accurate computations of the high-lying excited state manifold with dynamics simulations. Application is made to the two-dimensional electronic spectra of pyrene{,} a polycyclic aromatic hydrocarbon characterized by an ultrafast (few tens of femtosecond) decay from the bright S2 state to a dark S1 state. The spectra for waiting times t2 = 0 and t2 = 1 ps demonstrate the ability of this approach to model electronic state fluctuations and realistic lineshapes. Comparison with experimental spectra [Krebs et al.{,} New Journal of Physics{,} 2013{,} 15{,} 085016)] shows excellent agreement and allows to unambiguously assign the excited state absorption features."}
  • [DOI] R. Costard, T. Tyborski, B. P. Fingerhut, and T. Elsaesser, “Ultrafast phosphate hydration dynamics in bulk H2O,” J. Chem. Phys., vol. 142, p. 212406, 2015.
    [Bibtex]
    @article{Costard:2015,
    author = "Costard,Rene and Tyborski,Tobias and Fingerhut, Benjamin P. and Elsaesser, Thomas",
    title = "Ultrafast phosphate hydration dynamics in bulk H2O",
    journal = "J. Chem. Phys.",
    year = "2015",
    volume = "142",
    pages = "212406",
    doi = "10.1063/1.4914152",
    URL = "http://scitation.aip.org/content/aip/journal/jcp/142/21/10.1063/1.4914152",
    abstract=" Phosphate vibrations serve as local probes of hydrogen bonding and structural fluctuations
    of hydration shells around ions. Interactions of H$_2$PO$_4^-$ ions and their aqueous environment are studied combining femtosecond 2D infrared spectroscopy, ab-initio calculations, and hybrid quantum-classical molecular dynamics (MD) simulations. 2D IR spectra of the symmetric ($\nu_S$(PO$_2^-$)) and asymmetric ($\nu_{AS}$(PO$_2^-$)) PO$_2^-$ stretching vibrations display nearly homogeneous lineshapes and pronounced anharmonic couplings between the two modes and with the $\delta$(P-(OH)$_2$) bending modes. The frequency-time correlation function derived from the 2D spectra consists of a predominant 50 fs decay and a weak constant component accounting for a residual inhomogeneous broadening. MD simulations show that the fluctuating electric field of the aqueous environment induces strong fluctuations of the $\nu_S$(PO$_2^-$) and $\nu_{AS}$(PO$_2^-$) transition frequencies with larger frequency excursions for $\nu_{AS}$(PO$_2^-$). The calculated frequency-time correlation function is in good agreement with the experiment. The $\nu$(PO$_2^-$) frequencies are mainly determined by polarization contributions induced by electrostatic phosphate-water interactions.
    H$_2$PO$_4^-$/H$_2$O cluster calculations reveal substantial frequency shifts and mode mixing with increasing hydration. Predicted phosphate-water hydrogen bond (HB) lifetimes have values on the order of 10 ps, substantially longer than water-water HB lifetimes. The ultrafast phosphate-water interactions observed here are in marked contrast to hydration dynamics of phospholipids where a quasi-static inhomogeneous broadening of phosphate vibrations suggests minor structural fluctuations of interfacial water."
    }
  • [DOI] B. P. Fingerhut, K. E. Dorfman, and S. Mukamel, “Signatures of Conical Intersection Mediated Relaxation Dynamics in Time-Resolved Broadband Raman Detection,” in Ultrafast Phenomena XIX, K. Yamanouchi, S. Cundiff, R. de Vivie-Riedle, M. Kuwata-Gonokami, and L. Di Mauro, Eds., , 2015, vol. 162, pp. 419-423.
    [Bibtex]
    @incollection{Fingerhut:UP14,
    year={2015},
    isbn={978-3-540-95945-8},
    booktitle={Ultrafast Phenomena XIX},
    volume={162},
    series={Springer Proceedings in Physics},
    editor={Yamanouchi, K. and Cundiff, S. and de Vivie-Riedle, R. and Kuwata-Gonokami, M. and Di Mauro, L.},
    doi={http://www.springer.com/physics/complexity/book/978-3-319-13241-9},
    title={Signatures of Conical Intersection Mediated Relaxation Dynamics in Time-Resolved Broadband Raman Detection},
    url={http://www.springer.com/physics/complexity/book/978-3-319-13241-9}
    publisher={Springer, Heidelberg},
    author={Fingerhut, Benjamin P. and Dorfman, Konstantin E. and Mukamel, Shaul},
    pages={419-423},
    language={English},
    abstract = {Ab-Initio simulations of Raman signals reveal the excited state deactivation mechanism of uracil. The signals provide sub-molecular sensitivity of out-of-plane displacements during conical intersection mediated relaxation and properly describe the time-resolution of the techniques.}
    }

2014

  • [DOI] H. Ando, B. P. Fingerhut, K. E. Dorfman, J. D. Biggs, and S. Mukamel, “Femtosecond stimulated Raman spectroscopy of the cyclobutane thymine dimer repair mechanism: A computational study,” J. Am. Chem. Soc., vol. 136, iss. 42, pp. 14801-14810, 2014.
    [Bibtex]
    @article{doi:10.1021/ja5063955,
    author = {Ando, Hideo and Fingerhut, Benjamin P. and Dorfman, Konstantin E. and Biggs, Jason D. and Mukamel, Shaul},
    title = {Femtosecond stimulated Raman spectroscopy of the cyclobutane thymine dimer repair mechanism: A computational study},
    journal = {J. Am. Chem. Soc.},
    volume = {136},
    number = {42},
    pages = {14801-14810},
    year = {2014},
    doi = {10.1021/ja5063955},
    note ={PMID: 25238196},
    URL = {http://dx.doi.org/10.1021/ja5063955},
    eprint = {http://dx.doi.org/10.1021/ja5063955},
    abstract = { Cyclobutane thymine dimer, one of the major lesions in DNA formed by exposure to UV sunlight, is repaired in a photoreactivation process, which is essential to maintain life. The molecular mechanism of the central step, i.e., intradimer C-C bond splitting, still remains an open question. In a simulation study, we demonstrate how the time evolution of characteristic marker bands (C=O and C=C/C-C stretch vibrations) of cyclobutane thymine dimer and thymine dinucleotide radical anion, thymidylyl(3'$\rightarrow$5')thymidine, can be directly probed with femtosecond stimulated Raman spectroscopy (FSRS). We construct a DFT(M05-2X) potential energy surface with two minor barriers for the intradimer C5-C5' splitting and a main barrier for the C6-C6' splitting, and identify the appearance of two C5=C6 stretch vibrations due to the C6-C6' splitting as a spectroscopic signature of the underlying bond splitting mechanism. The sequential mechanism shows only absorptive features in the simulated FSRS signals, whereas the fast concerted mechanism shows characteristic dispersive lineshapes. }
    }
  • [DOI] B. P. Fingerhut, K. E. Dorfman, and S. Mukamel, “Probing the Conical Intersection Dynamics of the RNA Base Uracil by UV-Pump Stimulated-Raman Probe Signals; Ab Initio Simulations,” J. Chem. Theory Comput., vol. 10, iss. 3, pp. 1172-1188, 2014.
    [Bibtex]
    @article{doi:10.1021/ct401012u,
    author = "Fingerhut, Benjamin P. and Dorfman, Konstantin E. and Mukamel, Shaul",
    title = "Probing the Conical Intersection Dynamics of the RNA Base Uracil by UV-Pump Stimulated-Raman Probe Signals; Ab Initio Simulations",
    journal = "J. Chem. Theory Comput.",
    volume = "10",
    number = "3",
    pages = "1172-1188",
    year = "2014",
    doi = "10.1021/ct401012u",
    URL = "http://pubs.acs.org/doi/abs/10.1021/ct401012u",
    abstract ="Nonadiabatic electron and nuclear dynamics of photoexcited molecules involving conical intersections is of fundamental importance in many reactions such as the self-protection mechanism of DNA and RNA bases against UV irradiation. Nonlinear vibrational spectroscopy can provide an ultrafast sensitive probe for these processes. We employ a simulation protocol that combines nonadiabatic on-the-fly molecular dynamics with a mode-tracking algorithm for the simulation of femtosecond stimulated Raman spectroscopy (SRS) signals of the high frequency C-H- and N-H-stretch vibrations of the photoexcited RNA base uracil. The simulations rely on a microscopically derived expression that takes into account the path integral of the excited state evolution and the pulse shapes. Analysis of the joint time/frequency resolution of the technique reveals a matter chirp contribution that limits the inherent temporal resolution. Characteristic signatures of relaxation dynamics mediated in the vicinity of conical intersection are predicted. The C-H and N-H spectator modes provide high sensitivity to their local environment and act as local probes with submolecular and high temporal resolution."
    }

2013

  • [DOI] K. E. Dorfman, B. P. Fingerhut, and S. Mukamel, “Time-resolved broadband Raman spectroscopies: A unified six-wave-mixing representation,” J. Chem. Phys., vol. 139, iss. 12, p. 124113, 2013.
    [Bibtex]
    @article{:/content/aip/journal/jcp/139/12/10.1063/1.4821228,
    author = "Dorfman, Konstantin E. and Fingerhut, Benjamin P. and Mukamel, Shaul",
    title = "Time-resolved broadband Raman spectroscopies: A unified six-wave-mixing representation",
    journal = "J. Chem. Phys.",
    year = "2013",
    volume = "139",
    number = "12",
    eid = 124113,
    pages = "124113",
    url = "http://scitation.aip.org/content/aip/journal/jcp/139/12/10.1063/1.4821228",
    doi = "10.1063/1.4821228" ,
    abstract="Excited-state vibrational dynamics in molecules can be studied by an electronically off-resonant Raman process induced by a probe pulse with variable delay with respect to an actinic pulse. We establish the connection between several variants of the technique that involve either spontaneous or stimulated Raman detection and different pulse configurations. By using loop diagrams in the frequency domain, we show that all signals can be described as six wave mixing which depend on the same four point molecular correlation functions involving two transition dipoles and two polarizabilities and accompanied by a different gating. Simulations for the stochastic two-state-jump model illustrate the origin of the absorptive and dispersive features observed experimentally."
    }
  • [DOI] B. P. Fingerhut, K. E. Dorfman, and S. Mukamel, “Monitoring Nonadiabatic Dynamics of the RNA Base Uracil by UV Pump – IR Probe Spectroscopy,” J. Phys. Chem. Lett., vol. 4, iss. 11, pp. 1933-1942, 2013.
    [Bibtex]
    @article{doi:10.1021/jz400776r,
    author = {Fingerhut, Benjamin P. and Dorfman, Konstantin E. and Mukamel, Shaul},
    title = {Monitoring Nonadiabatic Dynamics of the RNA Base Uracil by UV Pump - IR Probe Spectroscopy},
    journal = {J. Phys. Chem. Lett.},
    volume = {4},
    number = {11},
    pages = {1933-1942},
    year = {2013},
    doi = {10.1021/jz400776r},
    URL = {http://pubs.acs.org/doi/abs/10.1021/jz400776r},
    eprint = {http://pubs.acs.org/doi/pdf/10.1021/jz400776r},
    abstract = { Resolving the excited-state dynamics of DNA and RNA nucleobases has attracted considerable attention. UV irradiation of the isolated nucleobases leads to the population of an electronic excited state, which is quenched by internal conversion mediated by conical intersections on an ultrafast time scale. We present nonadiabatic on-the-fly molecular dynamics simulations of the UV pump - IR probe signal of the pyrimidine nucleobase uracil using a novel semiclassical protocol that takes into account the path integral over the excited-state vibrational dynamics and properly describes the joint temporal and spectral resolution of the technique. Simulations of vibrational motions of carbonyl fingerprint modes in the electronically excited states reveal clear signatures of different relaxation pathways on a time scale of hundreds of femtoseconds, which arise from an ultrafast branching in the excited state. We show that the inherent temporal and spectral resolution of the technique is not purely instrumental but also depends on the vibrational fluctuation time scale. }
    }
  • [DOI] K. E. Dorfman, B. P. Fingerhut, and S. Mukamel, “Broadband infrared and Raman probes of excited-state vibrational molecular dynamics: simulation protocols based on loop diagrams,” Phys. Chem. Chem. Phys., vol. 15, pp. 12348-12359, 2013.
    [Bibtex]
    @Article{C3CP51117K,
    author ="Dorfman, Konstantin E. and Fingerhut, Benjamin P. and Mukamel, Shaul",
    title ="Broadband infrared and Raman probes of excited-state vibrational molecular dynamics: simulation protocols based on loop diagrams",
    journal ="Phys. Chem. Chem. Phys.",
    year ="2013",
    volume ="15",
    issue ="29",
    pages ="12348-12359",
    publisher ="The Royal Society of Chemistry",
    doi ="10.1039/C3CP51117K",
    url ="http://dx.doi.org/10.1039/C3CP51117K",
    abstract ="Vibrational motions in electronically excited states can be observed either by time and frequency resolved infrared absorption or by off resonant stimulated Raman techniques. Multipoint correlation function expressions are derived for both signals. Three representations which suggest different simulation protocols for the signals are developed. These are based on the forward and the backward propagation of the wavefunction{,} sum over state expansion using an effective vibrational Hamiltonian or a semiclassical treatment of a bath. We show that the effective temporal ([capital Delta]t) and spectral ([capital Delta][small omega]) resolution of the techniques is not controlled solely by experimental knobs but also depends on the system dynamics being probed. The Fourier uncertainty [capital Delta][small omega][capital Delta]t > 1 is never violated."}
  • [DOI] F. Schlawin, K. E. Dorfman, B. P. Fingerhut, and S. Mukamel, “Suppression of population transport and control of exciton distributions by entangled photons,” Nat. Commun., vol. 4, p. 1782, 2013.
    [Bibtex]
    @article{NatCom,
    author = "Schlawin, Frank and Dorfman, Konstantin E. and Fingerhut, Benjamin P. and Mukamel, Shaul",
    title = "Suppression of population transport and control of exciton distributions by entangled photons",
    journal = "Nat. Commun.",
    year = "2013",
    volume = "4",
    pages = "1782",
    url = "http://www.nature.com/ncomms/journal/v4/n4/full/ncomms2802.html",
    doi = "10.1038/ncomms2802",
    abstract ="Entangled photons provide an important tool for secure quantum communication, computing and lithography. Low intensity requirements for multi-photon processes make them idealy suited for minimizing damage in imaging applications. Here we show how their unique temporal and spectral features may be used in nonlinear spectroscopy to reveal properties of multiexcitons in chromophore aggregates. Simulations demostrate that they provide unique control tools for two-exciton states in the bacterial reaction centre of Blastochloris viridis. Population transport in the intermediate single-exciton manifold may be suppressed by the absorption of photon pairs with short entanglement time, thus allowing the manipulation of the distribution of two-exciton states. The quantum nature of the light is essential for achieving this degree of control, which cannot be reproduced by stochastic or chirped light. Classical light is fundamentally limited by the frequency-time uncertainty, whereas entangled photons have independent temporal and spectral characteristics not subjected to this uncertainty."
    }
  • [DOI] O. Roslyak, B. P. Fingerhut, K. Bennett, and S. Mukamel, “Quasiparticle representation of coherent nonlinear optical signals of multi-excitons,” New J. Phys., vol. 15, iss. 8, p. 83049, 2013.
    [Bibtex]
    @article{1367-2630-15-8-083049,
    author={Oleksiy Roslyak and Benjamin P Fingerhut and Kochise Bennett and Shaul Mukamel},
    title={Quasiparticle representation of coherent nonlinear optical signals of multi-excitons},
    journal={New J. Phys.},
    volume={15},
    number={8},
    pages={083049},
    url={http://www.iopscience.iop.org/1367-2630/15/8/083049},
    year={2013},
    doi = "10.1088/1367-2630/15/8/083049",
    abstract={Multi-exciton Green's functions and scattering matrices in many-fermion systems are calculated using a quasiparticle approach based on a generalized Bethe-Salpeter equation. The simulation protocol only requires numerical diagonalization of the single-exciton manifold. Using coboson algebra all many-body effects are recast in terms of two tetradic exciton-exciton interactions: direct Coulomb scattering and Pauli exchange. The tedious equations-of-motion derivations and calculations of multi-exciton manifolds are avoided. The approach is applied to calculate the third- and fifth-order signals generated by sequences of femtosecond optical pulses. Several coherent fifth order optical signals that directly probe three-exciton states and their projections on double and single-exciton states are predicted.}
    }
  • [DOI] S. Thallmair, B. P. Fingerhut, and R. de Vivie-Riedle, “Ground and Excited State Surfaces for the Photochemical Bond Cleavage in Phenylmethylphenylphosphonium Ions,” J. Phys. Chem. A, vol. 117, iss. 41, pp. 10626-10633, 2013.
    [Bibtex]
    @article{doi:10.1021/jp403082r,
    author = {Thallmair, Sebastian and Fingerhut, Benjamin P. and de Vivie-Riedle, Regina},
    title = {Ground and Excited State Surfaces for the Photochemical Bond Cleavage in Phenylmethylphenylphosphonium Ions},
    journal = {J. Phys. Chem. A},
    volume = {117},
    number = {41},
    pages = {10626-10633},
    year = {2013},
    doi = {10.1021/jp403082r},
    URL = {http://pubs.acs.org/doi/abs/10.1021/jp403082r},
    eprint = {http://pubs.acs.org/doi/pdf/10.1021/jp403082r},
    abstract = { Photolytic bond cleavage is a well-established method to generate carbocations for organic synthesis. Changes in the leaving group have a large influence on the chemical yield. The underlying potential energy surfaces governing the initial process are mostly unknown. We provide potential energy surfaces of ground and excited states on the CASSCF/CASPT2 level of theory for the charged precursor phenylmethylphenylphosphonium ion. We present the electronic and structural changes accompanying the excitation process and the subsequent bond cleavage. Inter-ring charge-transfer processes play a crucial role in the Franck-Condon region. Beyond the Franck-Condon region, competing reaction pathways emerge connected through conical intersections. The phenylmethylphenylphosphonium ion is used as a model system for the commonly used diphenylmethyltriphenylphosphonium ion. The appropriateness of the model is tested by CC2 calculations of the excitation spectrum. }
    }
  • [DOI] B. P. Fingerhut, K. Bennett, O. Roslyak, and S. Mukamel, “Selective Assignment of Energy Transfer and Charge Separation Pathways in Reaction Centers by Pulse Polarized 2-D Photon Echo Spectroscopy,” EPJ Web of Conferences, vol. 41, p. 7014, 2013.
    [Bibtex]
    @article{ refId0,
    author = {Fingerhut, Benjamin P. and Bennett, Kochise and Roslyak, Oleksiy and Mukamel, Shaul},
    title = {Selective Assignment of Energy Transfer and Charge Separation Pathways in Reaction Centers by Pulse Polarized 2-D Photon Echo Spectroscopy},
    DOI= "10.1051/epjconf/20134107014",
    url= "http://dx.doi.org/10.1051/epjconf/20134107014",
    journal = {EPJ Web of Conferences},
    year = 2013,
    volume = 41,
    pages = "07014",
    abstract = "We present theoretical modelling of the nonlinear optical response of the bacterial reaction center incorporating electron and energy transfer on equal footing. Orthogonal polarized pulse sequences allow to dissect kinetic components in real space."
    }
  • [DOI] W. Zinth, B. P. Fingerhut, T. T. Herzog, G. R. Ryseck, K. Haiser, F. F. Graupner, K. Heil, P. Gilch, W. J. Schreier, T. Carell, and R. de Vivie-Riedle, “Ultrafast spectroscopy of UV-induced DNA-lesions – on the search for strategies which keep DNA alive,” EPJ Web of Conferences, vol. 41, p. 7005, 2013.
    [Bibtex]
    @article{ refId1,
    author = {Zinth, W. and Fingerhut, B. P. and Herzog, T. T. and Ryseck, G. R. and Haiser, K. and Graupner, F. F. and Heil, K. and Gilch, P. and Schreier, W. J. and Carell, T. and de Vivie-Riedle, R.},
    title = {Ultrafast spectroscopy of UV-induced DNA-lesions - on the search for strategies which keep DNA alive},
    DOI= "10.1051/epjconf/20134107005",
    url= "http://dx.doi.org/10.1051/epjconf/20134107005",
    journal = {EPJ Web of Conferences},
    year = 2013,
    volume = 41,
    pages = "07005",
    abstract = "UV-induced photolesions are studied in the visible and IR. While structural distortions of the DNA-backbone at the moment of light absorption are prerequisite for CPD-formation, strain from the backbone guides Dewar-formation."
    }
  • [DOI] S. Thallmair, M. Kowalewski, B. P. Fingerhut, C. F. Sailer, and R. de Vivie-Riedle, “Molecular wave packet dynamics decelerated by solvent environment: A theoretical approach,” EPJ Web of Conferences, vol. 41, p. 5043, 2013.
    [Bibtex]
    @article{ refId2,
    author = {Thallmair, S. and Kowalewski, M. and Fingerhut, B.P. and Sailer, C.F. and de Vivie-Riedle, R.},
    title = {Molecular wave packet dynamics decelerated by solvent environment: A theoretical approach},
    DOI= "10.1051/epjconf/20134105043",
    url= "http://dx.doi.org/10.1051/epjconf/20134105043",
    journal = {EPJ Web of Conferences},
    year = 2013,
    volume = 41,
    pages = "05043",
    abstract = "We present a new dynamic continuum ansatz to describe the frictional force exerted on moving wave packets in a solvent cage. The solvent interferes on the femtosecond time scale, but decides the reaction outcome."
    }
  • [DOI] C. F. Sailer, N. Krebs, B. P. Fingerhut, R. de Vivie-Riedle, and E. Riedle, “Wavepacket Splitting in the First 100 fs Determines the Products from the Bond Cleavage of Diphenylmethylchloride,” EPJ Web of Conferences, vol. 41, p. 5042, 2013.
    [Bibtex]
    @article{ refId3,
    author = {Sailer, C.F. and Krebs, N. and Fingerhut, B.P. and de Vivie-Riedle, R. and Riedle, E.},
    title = {Wavepacket Splitting in the First 100 fs Determines the Products from the Bond Cleavage of Diphenylmethylchloride},
    DOI= "10.1051/epjconf/20134105042",
    url= "http://dx.doi.org/10.1051/epjconf/20134105042",
    journal = {EPJ Web of Conferences},
    year = 2013,
    volume = 41,
    pages = "05042",
    abstract = "An elementary chemical reaction proceeds through two distinct conical intersections. Benzhydryl radicals are formed with a delay of 80 fs, cations after 125 fs. The optical signal increases more slowly due to planarization and solvation."
    }
  • [DOI] C. F. Sailer, S. Thallmair, B. P. Fingerhut, C. Nolte, J. Ammer, H. Mayr, I. Pugliesi, R. de Vivie-Riedle, and E. Riedle, “A Comprehensive Microscopic Picture of the Benzhydryl Radical and Cation Photogeneration and Interconversion through Electron Transfer,” ChemPhysChem, vol. 14, iss. 7, pp. 1423-1437, 2013.
    [Bibtex]
    @article{CPHC:CPHC201201057,
    author = {Sailer, Christian F. and Thallmair, Sebastian and Fingerhut, Benjamin P. and Nolte, Christoph and Ammer, Johannes and Mayr, Herbert and Pugliesi, Igor and de Vivie-Riedle, Regina and Riedle, Eberhard},
    title = {A Comprehensive Microscopic Picture of the Benzhydryl Radical and Cation Photogeneration and Interconversion through Electron Transfer},
    journal = {ChemPhysChem},
    volume = {14},
    number = {7},
    publisher = {WILEY-VCH Verlag},
    issn = {1439-7641},
    url = {http://dx.doi.org/10.1002/cphc.201201057},
    doi = {10.1002/cphc.201201057},
    pages = {1423--1437},
    keywords = {carbocations, electron transfer, ion pairs, reaction mechanisms, time-resolved spectroscopy},
    year = {2013},
    abstract = {Bond cleavage and bond formation are central to organic chemistry. Carbocations play a key role in our understanding of nucleophilic substitution reactions that involve both processes. The precise understanding of the mechanism and dynamics of the photogeneration of carbocations and carbon radicals is therefore an important quest. In particular, the role of electron transfer for the generation of carbocations from the radical pair is still unclear. A quantitative femtosecond absorption study is presented, with ultrabroad probing on selected donor and acceptor substituted benzhydryl chlorides irradiated with 270 nm (35 fs) pulses. The ultrafast bond cleavage within 300 fs is almost exclusively homolytic, thus leading to a radical pair. The carbocations observable in the nanosecond regime are generated from these radicals by electron transfer from the benzhydryl to the chlorine radical within the first tens of picoseconds. Their concentration is reduced by geminate recombination within hundreds of picoseconds. In moderately polar solvents this depletion almost extinguishes the cation population; in highly polar solvents free ions are still observable on the nanosecond timescale. The explanation of the experimental findings requires the microscopic realm of the intermediates to be accounted for, including their spatial and environmental distributions. The distance dependent electron transfer described by Marcus theory is combined with Smoluchowski diffusion. The depletion of the radical pair distribution at small distances causes a temporal increase of the mean distance and the observed stretched exponential electron transfer. A close accord with experiment can only be reached for a broad distribution of the nascent radical pairs. The increase in the inter-radical and inter-ion pair distance is measured directly as a shift of the UV/Vis absorption of the products. The results demonstrate that, at least for aprotic solvents, traditional descriptions of reaction mechanisms based on the concept of contact and solvent-separated pairs have to be reassessed.},
    }
  • [DOI] H. Ren, B. P. Fingerhut, and S. Mukamel, “Time Resolved Photoelectron Spectroscopy of Thioflavin T Photoisomerization: A Simulation Study,” J. Phys. Chem. A, vol. 117, iss. 29, pp. 6096-6104, 2013.
    [Bibtex]
    @article{doi:10.1021/jp400044t,
    author = {Ren, Hao and Fingerhut, Benjamin P. and Mukamel, Shaul},
    title = {Time Resolved Photoelectron Spectroscopy of Thioflavin T Photoisomerization: A Simulation Study},
    journal = {J. Phys. Chem. A},
    volume = {117},
    number = {29},
    pages = {6096-6104},
    year = {2013},
    doi = {10.1021/jp400044t},
    URL = {http://pubs.acs.org/doi/abs/10.1021/jp400044t},
    eprint = {http://pubs.acs.org/doi/pdf/10.1021/jp400044t},
    abstract = {The excited state isomerization of thioflavin T (ThT) is responsible for the quenching of its fluorescence in a nonrestricted environment. The fluorescence quantum yield increases substantially upon binding to amyloid fibers. Simulations reveal that the variation of the twisting angle between benzothiazole and benzene groups ($\phi_1$) is responsible for the subpicosecond fluorescence quenching. The evolution of the twisting process can be directly probed by photoelectron emission with energies $\epsilon \ge$ 1.0 eV before the molecule reaches the $\phi_1$-twisted configuration (300 fs).}
    }
  • [DOI] B. P. Fingerhut, M. Richter, J. Luo, A. Zunger, and S. Mukamel, “2D optical photon echo spectroscopy of a self-assembled quantum dot,” Ann. Phys., vol. 525, iss. 1-2, pp. 31-42, 2013.
    [Bibtex]
    @article{ANDP:ANDP201200204,
    author = {Fingerhut, Benjamin P. and Richter, Marten and Luo, Jun-Wei and Zunger, Alex and Mukamel, Shaul},
    title = {2D optical photon echo spectroscopy of a self-assembled quantum dot},
    journal = {Ann. Phys.},
    volume = {525},
    number = {1-2},
    issn = {1521-3889},
    url = {http://dx.doi.org/10.1002/andp.201200204},
    doi = {10.1002/andp.201200204},
    pages = {31--42},
    keywords = {Self-assembled quantum dots, non-linear optical spectroscopy, many-body effects},
    year = {2013},
    abstract = {Simulations of two dimensional coherent photon echo (2D-PE) spectra of self-assembled InAs/GaAs quantum dots (QD) in different charged states are presented revealing the coupling between the individual mono-exciton Xq transitions and contributions of bi-excitons XXq. The information about the XXq states is crucial for various application scenarios of QDs, like e.g. highly efficient solar cells. The simulations rely on a microscopic description of the electronic structure by high-level atomistic many-body pseudopotential calculations. It is shown that asymmetric diagonal peak shapes and double cross-peaks are the result of XXq state contributions to the PE signal by analyzing the contributions of the individual pathways excited state emission, ground state bleach and excited state absorption. The results show that from the detuned Xq and XXq contributions the bi-exciton binding energies of the XXq manifold are revealed in 2D-PE signals.},
    }

2012

  • [DOI] B. P. Fingerhut, M. Richter, J. Luo, A. Zunger, and S. Mukamel, “Dissecting biexciton wave functions of self-assembled quantum dots by double-quantum-coherence optical spectroscopy,” Phys. Rev. B, vol. 86, p. 235303, 2012.
    [Bibtex]
    @article{PhysRevB.86.235303,
    title = {Dissecting biexciton wave functions of self-assembled quantum dots by double-quantum-coherence optical spectroscopy},
    author = {Fingerhut, Benjamin P. and Richter, Marten and Luo, Jun-Wei and Zunger, Alex and Mukamel, Shaul},
    journal = {Phys. Rev. B},
    volume = {86},
    issue = {23},
    pages = {235303},
    numpages = {10},
    year = {2012},
    month = {Dec},
    publisher = {American Physical Society},
    doi = {10.1103/PhysRevB.86.235303},
    url = {http://link.aps.org/doi/10.1103/PhysRevB.86.235303},
    abstract = {Biexcitons feature prominently in various scenarios for utilization of quantum dots (QDs) for enhancing the efficiencies of solar cells, and for the generation of entangled photon pairs in single QD sources. Two-dimensional double quantum coherence (2D-DQC) nonlinear optical spectra provide novel spectroscopic signatures of such states beyond global intensity and lifetime characteristics which are available by more conventional techniques. We report the simulation of a prototype 2D-DQC optical experiment of a self-assembled InAs/GaAs dot. The simulations consider the QD in different charged states and are based on a state-of-the-art atomistic many-body pseudopotential method for the calculation of the electronic structure and transition dipole matrix elements. Comparison of the spectra of negatively charged, neutral, and positively charged QD reveals optical signatures of their electronic excitations. This technique directly accesses the biexciton (XX) energies as well as the projections of their wave functions on the single-exciton manifold. These signals also provide a unique tool for probing the charged state of the QD and thus the occupation of the quantum state. Signatures of Pauli blockade of the creation of certain single and two excitons due to charges on the particles are observed. For all quantum states of the QD, the spectra reveal a strong multiconfiguration character of the biexciton wave functions. Peak intensities can be explained by interference of the contributing Liouville space pathways.}
    }
  • [DOI] F. Schlawin, K. E. Dorfman, B. P. Fingerhut, and S. Mukamel, “Manipulation of two-photon-induced fluorescence spectra of chromophore aggregates with entangled photons: A simulation study,” Phys. Rev. A, vol. 86, p. 23851, 2012.
    [Bibtex]
    @article{PhysRevA.86.023851,
    title = {Manipulation of two-photon-induced fluorescence spectra of chromophore aggregates with entangled photons: A simulation study},
    author = {Schlawin, Frank and Dorfman, Konstantin E. and Fingerhut, Benjamin P. and Mukamel, Shaul},
    journal = {Phys. Rev. A},
    volume = {86},
    issue = {2},
    pages = {023851},
    numpages = {10},
    year = {2012},
    month = {Aug},
    publisher = {American Physical Society},
    doi = {10.1103/PhysRevA.86.023851},
    url = {http://link.aps.org/doi/10.1103/PhysRevA.86.023851},
    abstract = {The nonclassical spectral and temporal features of entangled photons offer new possibilities to investigate the interactions of excitons in photosynthetic complexes and to target the excitation of specific states. Simulations of fluorescence in the bacterial reaction center induced by entangled light demonstrate a degree of selectivity of double-exciton states which is not possible using classical stochastic light with the same power spectrum.}
    }
  • [DOI] B. P. Fingerhut and S. Mukamel, “Resolving the Electron Transfer Kinetics in the Bacterial Reaction Center by Pulse Polarized 2-D Photon Echo Spectroscopy,” J. Phys. Chem. Lett., vol. 3, iss. 13, pp. 1798-1805, 2012.
    [Bibtex]
    @article{doi:10.1021/jz3006282,
    author = {Fingerhut, Benjamin P. and Mukamel, Shaul},
    title = {Resolving the Electron Transfer Kinetics in the Bacterial Reaction Center by Pulse Polarized 2-D Photon Echo Spectroscopy},
    journal = {J. Phys. Chem. Lett.},
    volume = {3},
    number = {13},
    pages = {1798-1805},
    year = {2012},
    doi = {10.1021/jz3006282},
    URL = {http://pubs.acs.org/doi/abs/10.1021/jz3006282},
    eprint = {http://pubs.acs.org/doi/pdf/10.1021/jz3006282},
    abstract = { At the heart of photosynthesis is excitation energy transfer toward and charge separation within highly conserved reaction centers (RCs). The function principles of RCs in purple bacteria offer a blueprint for an optoelectronic device, which efficiently utilizes the near-IR region of the solar spectrum. We present theoretical modeling of the nonlinear optical response of the bacterial RC B. viridis incorporating electron and energy transfer on equal footing. The splitting of special pair excitons P is the origin of distinct cross peaks, which allow monitoring of the kinetics of charge separation. The xxyy - xyxy signal, obtained from sequences of orthogonal polarized laser pulses, highlights the kinetics of the secondary, subpicosecond electron transfer from the accessory bacteriochlorophyll BClL to the bacteriopheophytine BPL. The increased selectivity is explained by the relative orientation of exciton transitions. The technique can resolve complex kinetics in congested signals of photosynthetic complexes that are otherwise hardly accessible. }
    }
  • [DOI] B. P. Fingerhut, K. Heil, E. Kaya, S. Oesterling, R. de Vivie-Riedle, and T. Carell, “Mechanism of UV-induced Dewar lesion repair catalysed by DNA (6-4) photolyase,” Chem. Sci., vol. 3, pp. 1794-1797, 2012.
    [Bibtex]
    @Article{C2SC20122D,
    author ="Fingerhut, Benjamin P. and Heil, Korbinian and Kaya, Emine and Oesterling, Sven and de Vivie-Riedle, Regina and Carell, Thomas",
    title ="Mechanism of UV-induced Dewar lesion repair catalysed by DNA (6-4) photolyase",
    journal ="Chem. Sci.",
    year ="2012",
    volume ="3",
    issue ="6",
    pages ="1794-1797",
    publisher ="The Royal Society of Chemistry",
    doi ="10.1039/C2SC20122D",
    url ="http://dx.doi.org/10.1039/C2SC20122D",
    abstract ="UV irradiation of cellular DNA leads to the formation of mutagenic pyrimidine derived dimer lesions. One of the stable end products of the lesion forming pathways are DNA Dewar lesions. Here we report that the TpC derived Dewar lesions are efficiently repaired by the repair enzyme (6-4) photolyase, while the TpT derived Dewar lesion is unrepairable. We provide experimental and theoretical data showing that the substituent of the Dewar substructure is mainly responsible for this behavior. Studies with synthetic derivatives of the Dewar lesions and theory reveal how the substitution pattern of the important Dewar lesions governs their reparability."}
  • [DOI] B. P. Fingerhut, T. T. Herzog, G. Ryseck, K. Haiser, F. F. Graupner, K. Heil, P. Gilch, W. J. Schreier, T. Carell, R. de Vivie-Riedle, and W. Zinth, “Dynamics of ultraviolet-induced DNA lesions: Dewar formation guided by pre-tension induced by the backbone,” New J. Phys., vol. 14, iss. 6, p. 65006, 2012.
    [Bibtex]
    @article{1367-2630-14-6-065006,
    author={B P Fingerhut and T T Herzog and G Ryseck and K Haiser and F F Graupner and K Heil and P Gilch and W J Schreier and T Carell and R de
    Vivie-Riedle and W Zinth},
    title={Dynamics of ultraviolet-induced DNA lesions: Dewar formation guided by pre-tension induced by the backbone},
    journal={New J. Phys.},
    volume={14},
    number={6},
    pages={065006},
    url={http://stacks.iop.org/1367-2630/14/i=6/a=065006},
    year={2012},
    doi = {10.1088/1367-2630/14/6/065006},
    abstract={The photophysical and photochemical processes driving the formation of the ultraviolet (UV)-induced DNA Dewar lesion from the T(6-4)T dimer are investigated by time-resolved spectroscopy and quantum chemical modelling. Time-resolved absorption and emission spectroscopy in the UV revealed a biexponential decay of the electronically excited state (S 1 ) with time constants in the 100 ps and 1 ns range. From the S 1 state the system forms the Dewar lesion (proven by time-resolved infrared spectroscopy), the triplet state of the T(6-4)T dimer and the ground state of the original T(6-4)T dimer. The decay process from the excited singlet is activated and thus temperature dependent. Quantum chemical modelling is used to describe the reaction path via a minimum on the excited electronic potential energy surface in close proximity to a triplet state. The transition to the Dewar isomer competes with internal conversion and with triplet formation. Only if the backbone between the two thymines is closed, is the Dewar isomer formed with a significant yield. The simulations reveal that the tension built up by the backbone is required for guiding the reaction to the conical intersection leading to the Dewar isomer.}
    }
  • [DOI] B. P. Fingerhut, S. Oesterling, K. Haiser, K. Heil, A. Glas, W. J. Schreier, W. Zinth, T. Carell, and R. de Vivie-Riedle, “ONIOM approach for non-adiabatic on-the-fly molecular dynamics demonstrated for the backbone controlled Dewar valence isomerization,” J. Chem. Phys., vol. 136, iss. 20, p. 204307, 2012.
    [Bibtex]
    @article{:/content/aip/journal/jcp/136/20/10.1063/1.4720090,
    author = "Fingerhut, Benjamin P. and Oesterling, Sven and Haiser, Karin and Heil, Korbinian and Glas, Andreas and Schreier, Wolfgang J. and Zinth, Wolfgang and Carell, Thomas and de Vivie-Riedle, Regina",
    title = "ONIOM approach for non-adiabatic on-the-fly molecular dynamics demonstrated for the backbone controlled Dewar valence isomerization",
    journal = "J. Chem. Phys.",
    year = "2012",
    volume = "136",
    number = "20",
    eid = 204307,
    pages = "204307",
    url = "http://scitation.aip.org/content/aip/journal/jcp/136/20/10.1063/1.4720090",
    doi = "10.1063/1.4720090",
    abstract = "Non-adiabatic on-the-fly molecular dynamics (NA-O-MD) simulations require the electronic wavefunction,energy gradients, and derivative coupling vectors in every timestep. Thus, they are commonly restricted to the excited statedynamics of molecules with up to $\approx$ 20 atoms. We discuss an approximation that combines the ONIOM(QM:QM) method with NA-O-MD simulations to allow calculations for larger molecules. As a proof of principle we present the excited statedynamics of a (6-4)-lesion containing dinucleotide (63 atoms), and especially the importance to include the confinement effects of the DNA backbone. The method is able to include electron correlation on a high level of theory and offers an attractive alternative to QM:MM approaches for moderate sized systems with unknown force fields."
    }
  • [DOI] B. P. Fingerhut, C. F. Sailer, J. Ammer, E. Riedle, and R. de Vivie-Riedle, “Buildup and Decay of the Optical Absorption in the Ultrafast Photo-Generation and Reaction of Benzhydryl Cations in Solution,” J. Phys. Chem. A, vol. 116, iss. 46, pp. 11064-11074, 2012.
    [Bibtex]
    @article{doi:10.1021/jp300986t,
    author = {Fingerhut, Benjamin P. and Sailer, Christian F. and Ammer, Johannes and Riedle, Eberhard and de Vivie-Riedle, Regina},
    title = {Buildup and Decay of the Optical Absorption in the Ultrafast Photo-Generation and Reaction of Benzhydryl Cations in Solution},
    journal = {J. Phys. Chem. A},
    volume = {116},
    number = {46},
    pages = {11064-11074},
    year = {2012},
    doi = {10.1021/jp300986t},
    URL = {http://pubs.acs.org/doi/abs/10.1021/jp300986t},
    eprint = {http://pubs.acs.org/doi/pdf/10.1021/jp300986t},
    abstract = { The identification of the transition state or a short-lived intermediate of a chemical reaction is essential for the understanding of the mechanism. For a direct identification typically transient optical spectroscopy is used, preferentially with high temporal resolution. We combine broad-band femtosecond transient absorption measurements and on-the-fly molecular dynamics calculations to decipher the microscopic evolution of the geometry and solvation of photogenerated benzhydryl cations (Ar2CH+, Ar = phenyl, p-tolyl, m-fluorophenyl, or m,m'-difluorophenyl) in bulk solution. From the high level quantum chemical calculations on the microsolvated cation we can deduce a narrowing and blue shift of the cation absorption that is nearly quantitatively equal to the experimental finding. The roughly 300 fs initial increase in the absorption signal found for all investigated combinations of benzhydryl chlorides or phosphonium salts as benzhydryl cation precursors and solvents is therefore assigned to the planarization and solvation of the nascent fragment of the bond cleavage. The actual cleavage time cannot directly be deduced from the rise of the spectroscopic signal. For alcohols as solvent, the cation combines on the picosecond time scale either with one of the solvent molecules to the ether or to a lesser degree geminately with the leaving group. The study shows that the absorption signal attributable to a species like the benzhydryl cation does not mirror the concentration during the first instances of the process. Rather, the signal is determined by the geometrical relaxation of the photoproduct and the response of the solvent. }
    }
  • [DOI] K. Haiser, B. P. Fingerhut, K. Heil, A. Glas, T. T. Herzog, B. M. Pilles, W. J. Schreier, W. Zinth, R. deVivie-Riedle, and T. Carell, “Mechanism of UV-Induced Formation of Dewar Lesions in DNA,” Angew. Chem. Int. Ed., vol. 51, iss. 2, pp. 408-411, 2012.
    [Bibtex]
    @article{ANIE:ANIE201106231,
    author = {Haiser, Karin and Fingerhut, Benjamin P. and Heil, Korbinian and Glas, Andreas and Herzog, Teja T. and Pilles, Bert M. and Schreier, Wolfgang J. and Zinth, Wolfgang and deVivie-Riedle, Regina and Carell, Thomas},
    title = {Mechanism of UV-Induced Formation of Dewar Lesions in DNA},
    journal = {Angew. Chem. Int. Ed.},
    volume = {51},
    number = {2},
    publisher = {WILEY-VCH Verlag},
    issn = {1521-3773},
    url = {http://dx.doi.org/10.1002/anie.201106231},
    doi = {10.1002/anie.201106231},
    pages = {408--411},
    keywords = {ab initio calculations, Dewar valence isomer, DNA damage, time-resolved IR spectroscopy, UV irradiation},
    year = {2012},
    abstract = {The mechanism of formation of Dewar lesions (see scheme) has been investigated by using femtosecond IR spectroscopy and ab initio calculations of the exited state. The 4$\pi$?electrocyclization is rather slow, occurs with an unusual high quantum yield, and - surprisingly - is controlled by the phosphate backbone.}
    }
  • [DOI] K. Haiser, B. P. Fingerhut, K. Heil, A. Glas, T. T. Herzog, B. M. Pilles, W. J. Schreier, W. Zinth, R. de-Vivie-Riedle, and T. Carell, “Mechanismus der UV-induzierten Bildung von Dewar-Schaeden in DNA,” Angew. Chem., vol. 124, iss. 2, pp. 421-424, 2012.
    [Bibtex]
    @article{ANGE:ANGE201106231-1,
    author = {Haiser, Karin and Fingerhut, Benjamin P. and Heil, Korbinian and Glas, Andreas and Herzog, Teja T. and Pilles, Bert M. and Schreier, Wolfgang J. and Zinth, Wolfgang and de-Vivie-Riedle, Regina and Carell, Thomas},
    title = {Mechanismus der UV-induzierten Bildung von Dewar-Schaeden in DNA},
    journal = {Angew. Chem.},
    volume = {124},
    number = {2},
    publisher = {WILEY-VCH Verlag},
    issn = {1521-3757},
    url = {http://dx.doi.org/10.1002/ange.201106231},
    doi = {10.1002/ange.201106231},
    pages = {421--424},
    keywords = {Ab-initio-Rechnungen, Dewar-Valenzisomer, DNA-Schaden, UV-Bestrahlung, Zeitaufgeloeste IR-Spektroskopie},
    year = {2012},
    abstract = {Der Mechanismus der Bildung des Dewar-Schadens (siehe Schema) wurde mit Femtosekunden-IR-Spektroskopie und Ab-initio-Rechnungen des angeregten Zustands untersucht. Die 4$\pi$-Elektrocyclisierung verlaeuft relativ langsam, findet mit einer ungewoehnlich hohen Quantenausbeute statt und wird - ueberraschenderweise - durch das Phosphat-Rueckgrat kontrolliert.}
    }

2010

  • [DOI] B. P. Fingerhut, W. Zinth, and R. de Vivie-Riedle, “The detailed balance limit of photochemical energy conversion,” Phys. Chem. Chem. Phys., vol. 12, pp. 422-432, 2010.
    [Bibtex]
    @Article{B914552D,
    author ="Fingerhut, Benjamin P. and Zinth, Wolfgang and de Vivie-Riedle, Regina",
    title ="The detailed balance limit of photochemical energy conversion",
    journal ="Phys. Chem. Chem. Phys.",
    year ="2010",
    volume ="12",
    issue ="2",
    pages ="422-432",
    publisher ="The Royal Society of Chemistry",
    doi ="10.1039/B914552D",
    url ="http://dx.doi.org/10.1039/B914552D",
    abstract = "Limits and optimization of a solar energy conversion system consisting of a photochemical charge separating unit coupled to an energy storage state are explored by multi-objective genetic algorithms. Pareto fronts were evaluated to obtain information about the ideal parameter combinations, guaranteeing highest efficiency. The light absorbing and charge separating unit is described by a chain of chromophores and electron carriers, connected by Marcus type electron transfer processes. It is coupled to the thermal equilibrium of charge conduction and transport in an energy storage system according to the principle of detailed balance. In addition to our previous findings for an optimal charge separation unit, consisting of a minimum number of charge carriers with adapted recombination and reaction rates, the complete photochemical unit must fulfil further requirements. Low reorganization energies are found to be essential for the initial charge separation steps and can be realized by a low dielectric constant in the local environment. The identified optimal operation rates can be realized by antenna systems adapted to the illumination conditions. For standard solar illumination and a realistic parameter setting energy conversion efficiencies up to 26.8\% are predicted, comparable to the limit (31.8\%) of ideal single junction semiconductor solar cells."
    }
  • [DOI] B. P. Fingerhut, W. Zinth, and R. de Vivie-Riedle, “Optimization of the Fast Charge Separation in Artificial Photosynthesis for Efficient Transport,” in International Conference on Ultrafast Phenomena, 2010, p. WD3.
    [Bibtex]
    @inproceedings{Fingerhut:10,
    author = {Benjamin P. Fingerhut and Wolfgang Zinth and Regina de Vivie-Riedle},
    booktitle = {International Conference on Ultrafast Phenomena},
    journal = {International Conference on Ultrafast Phenomena},
    keywords = {Spectroscopy; Spectroscopy, time-resolved; Ultrafast optics; Picosecond phenomena},
    pages = {WD3},
    publisher = {Optical Society of America},
    title = {Optimization of the Fast Charge Separation in Artificial Photosynthesis for Efficient Transport},
    year = {2010},
    url = {http://www.opticsinfobase.org/abstract.cfm?URI=UP-2010-WD3},
    doi = {10.1364/UP.2010.WD3},
    abstract = {The concepts of bacterial photosynthesis are extended to the design of artificial photochemical devices. With multi-objective genetic algorithms we reveal the energetic, morphologic and kinetic requirements of an optimized charge-separating unit coupled to diffusive transport.}
    }
  • [DOI] C. F. Sailer, B. P. Fingerhut, J. Ammer, C. Nolte, I. Pugliesi, H. Mayr, R. de Vivie-Riedle, and E. Riedle, “The First Picoseconds in the Life of Benzhydryl Cations: Ultrafast Generation and Chemical Reactions,” in International Conference on Ultrafast Phenomena, 2010, p. ThE14.
    [Bibtex]
    @inproceedings{Sailer:10,
    author = {Christian F. Sailer and Benjamin P. Fingerhut and Johannes Ammer and Christoph Nolte and Igor Pugliesi and Herbert Mayr and Regina de Vivie-Riedle and Eberhard Riedle},
    booktitle = {International Conference on Ultrafast Phenomena},
    journal = {International Conference on Ultrafast Phenomena},
    keywords = {Physical optics; Photochemistry; Spectroscopy; Spectroscopy, ultrafast},
    pages = {ThE14},
    publisher = {Optical Society of America},
    title = {The First Picoseconds in the Life of Benzhydryl Cations: Ultrafast Generation and Chemical Reactions},
    year = {2010},
    url = {http://www.opticsinfobase.org/abstract.cfm?URI=UP-2010-ThE14},
    doi = {10.1364/UP.2010.ThE14},
    abstract = {For benzhydryl chloride compounds we observe that photodissociation only leads to radical pairs. The typically observed cations are formed by subsequent electron transfer. Reactions of cations in neat alcohols can then occur within 2.6 ps.}
    }

2009

  • [DOI] B. Fingerhut, W. Zinth, and R. Vivie-Riedle, “Electron Transfer in Photosynthetic Reaction Centers: Optimization in Model and Nature,” in Ultrafast Phenomena XVI, P. Corkum, S. Silvestri, K. A. Nelson, E. Riedle, and R. W. Schoenlein, Eds., Springer Berlin Heidelberg, 2009, vol. 92, pp. 571-573.
    [Bibtex]
    @incollection{UP2008,
    year={2009},
    isbn={978-3-540-95945-8},
    booktitle={Ultrafast Phenomena XVI},
    volume={92},
    series={Springer Series in Chemical Physics},
    editor={Corkum, Paul and Silvestri, Sandro and Nelson, Keith A. and Riedle, Eberhard and Schoenlein, Robert W.},
    doi={10.1007/978-3-540-95946-5_185},
    title={Electron Transfer in Photosynthetic Reaction Centers: Optimization in Model and Nature},
    url={http://dx.doi.org/10.1007/978-3-540-95946-5_185},
    publisher={Springer Berlin Heidelberg},
    author={Fingerhut, BenjaminP. and Zinth, Wolfgang and Vivie-Riedle, Regina},
    pages={571-573},
    language={English},
    abstract = {We discuss the principles of optimal charge separation processes in bacterial reaction centers. Non-adiabatic electron transfer (ET) theory is combined with a Darwinian optimization. Our results reveal that the ET cascade is stable with respect to severe perturbations in the last ET step to maintain efficient charge separation.}
    }

2008

  • [DOI] B. P. Fingerhut, W. Zinth, and R. de Vivie-Riedle, “Design criteria for optimal photosynthetic energy conversion,” Chem. Phys. Lett., vol. 466, iss. 4-6, pp. 209-213, 2008.
    [Bibtex]
    @article{Fingerhut2008209,
    title = "Design criteria for optimal photosynthetic energy conversion ",
    journal = "Chem. Phys. Lett.",
    volume = "466",
    number = "4-6",
    pages = "209 - 213",
    year = "2008",
    note = "",
    issn = "0009-2614",
    doi = "10.1016/j.cplett.2008.10.053",
    url = "http://www.sciencedirect.com/science/article/pii/S0009261408014218",
    author = "Benjamin P. Fingerhut and Wolfgang Zinth and Regina de Vivie-Riedle",
    abstract = "Photochemical solar energy conversion is considered as an alternative of clean energy. For future light converting nano-machines photosynthetic reaction centers are used as prototypes optimized during evolution. We introduce a reaction scheme for global optimization and simulate the ultrafast charge separation in photochemical energy conversion. Multiple molecular charge carriers are involved in this process and are linked by Marcus-type electron transfer. In combination with evolutionary algorithms, we unravel the biological strategies for high quantum efficiency in photosynthetic reaction centers and extend these concepts to the design of artificial photochemical devices for energy conversion."
    }
  • [DOI] B. P. Fingerhut, D. Geppert, and R. de Vivie-Riedle, “Ultrafast dissociation pathways of diphenylmethyl chloride to generate reactive carbo cations,” Chem. Phys., vol. 343, iss. 2-3, pp. 329-339, 2008.
    [Bibtex]
    @article{Fingerhut2008329,
    title = "Ultrafast dissociation pathways of diphenylmethyl chloride to generate reactive carbo cations ",
    journal = "Chem. Phys.",
    volume = "343",
    number = "2-3",
    pages = "329 - 339",
    year = "2008",
    note = "Theoretical Spectroscopy and its Impact on Experiment (in honour of Sigrid D. Peyerimhoff) ",
    issn = "0301-0104",
    doi = "10.1016/j.chemphys.2007.07.034",
    url = "http://www.sciencedirect.com/science/article/pii/S0301010407003199",
    author = "Benjamin P. Fingerhut and Dorothee Geppert and Regina de Vivie-Riedle",
    keywords = "Quantum dynamics",
    keywords = "Conical intersections",
    keywords = "Photodissociation",
    keywords = "Ab initio calculations of excited \{PES\}",
    keywords = "Carbo cations",
    keywords = "Charge transfer processes ",
    abstract = "The primary processes in the formation of electrophilic precursor ions are studied on a microscopic scale by quantum chemical and quantum dynamical methods. For the competing reaction channels of heterolysis and homolysis in the photochemically induced dissociation of diphenylmethyl chloride, ab initio data for the ground and excited electronic states are evaluated in the gas phase. Here, the simultaneous formation of ionic and radicalic products can solely be attributed to the existence of conical intersections which are localized and characterized for the first time. The interaction of different electronic states also leads to the initial charge transfer from the phenyl $\pi$-system to the $\sigma$-bond of the leaving group which is essential for the fast dissociation and is explained by orbital analysis. Quantum dynamical calculations in one and two dimensions suggest that in gas phase the ion pair constitutes the main product despite its higher potential energy. Possible changes in polar solvents, where the ionic fragments are stabilized below the radical channel, are discussed."
    }

2005

  • [DOI] L. T. Kaspar, B. Fingerhut, and L. Ackermann, “Titanium-Catalyzed Intermolecular Hydroamination of Vinylarenes,” Angew. Chem. Int. Ed., vol. 44, iss. 37, pp. 5972-5974, 2005.
    [Bibtex]
    @article{ANIE:ANIE200501423,
    author = {Kaspar, Ludwig T. and Fingerhut, Benjamin and Ackermann, Lutz},
    title = {Titanium-Catalyzed Intermolecular Hydroamination of Vinylarenes},
    journal = {Angew. Chem. Int. Ed.},
    volume = {44},
    number = {37},
    publisher = {WILEY-VCH Verlag},
    issn = {1521-3773},
    url = {http://dx.doi.org/10.1002/anie.200501423},
    doi = {10.1002/anie.200501423},
    pages = {5972--5974},
    keywords = {alkenes, catalysis, heterocycles, hydroamination, titanium},
    year = {2005},
    abstract = {The Lewis acid TiCl4 allows the intermolecular hydroamination of vinylarenes (see scheme). Some of the hydroamination products undergo rearrangements to give ortho-alkylated compounds. The catalyst tolerates a range of functional groups (R'=CF3, Cl, CN, F, Br) and provides the products in good yields. This method was also applied to the synthesis of a tetrahydroisoquinoline derivative.}
    }
  • [DOI] L. T. Kaspar, B. Fingerhut, and L. Ackermann, “Titan-katalysierte intermolekulare Hydroaminierung von Vinylarenen,” Angew. Chem., vol. 117, iss. 37, pp. 6126-6128, 2005.
    [Bibtex]
    @article{ANGE:ANGE200501423,
    author = {Kaspar, Ludwig T. and Fingerhut, Benjamin and Ackermann, Lutz},
    title = {Titan-katalysierte intermolekulare Hydroaminierung von Vinylarenen},
    journal = {Angew. Chem.},
    volume = {117},
    number = {37},
    publisher = {WILEY-VCH Verlag},
    issn = {1521-3757},
    url = {http://dx.doi.org/10.1002/ange.200501423},
    doi = {10.1002/ange.200501423},
    pages = {6126--6128},
    keywords = {Alkene, Heterocyclen, Hydroaminierungen, Katalyse, Titan},
    year = {2005},
    abstract = {Mit der Lewis-Saeure TiCl4 gelingt die intermolekulare Hydroaminierung von Vinylarenen (siehe Schema). Die Hydroaminierungsprodukte lagern sich anschliessend zum Teil zu ortho-alkylierten Verbindungen um. Der Katalysator toleriert unterschiedliche funktionelle Gruppen (R'=CF3, Cl, CN, F, Br) und liefert die Produkte in guter Ausbeute. Diese Methode ermoeglichte auch die Synthese eines Tetrahydroisochinolins.}
    }