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Controlling Coherent Quantum Nuclear Dynamics in LiH by Ultra Short IR Atto Pulses

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Progress in Ultrafast Intense Laser Science XIII

Part of the book series: Springer Series in Chemical Physics ((PUILS))

Abstract

We examine computationally how ultrashort polarized strong one cycle IR pulses can be used for steering coherent nuclear dynamics in LiH. The nuclear motion is described using the time-dependent Schrödinger equation on a grid for several coupled electronic states. The coupling to the strong field of the pump and probe pulses is included in the Hamiltonian as well as the non adiabatic coupling between the different electronic states. LiH possesses low lying Σ and Π states that can be selectively accessed by controlling the polarization of the pump pulse along the bond or perpendicularly to it. In addition, when using a one cycle pulse, controlling the carrier envelope phase (CEP) allows to select the states that will be coherently excited according to their polarity. Since some of the excited Σ states and all the Π states are repulsive, polarization and CEP control of the pump pulse leads to controlling the dissociation yields. In particular, our quantum dynamics simulations show that the ratio of the fragmentation yields of the Σ2 and Σ3 states can be changed by a factor 10 when the CEP of a one cycle IR pulse polarized along the bond is switched from 0 to π. In addition to probing the dynamics by following the fragmentation, we also report on probing the coherent vibronic wave packet using transient absorption spectra that results from the interaction of the molecular transition dipole with the electric fields of the pump and the probe pulses. The emission spectrum retrieves the different time scales of the vibronic dynamics and probes the time evolution of the coherences.

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References

  1. F. Remacle, R.D. Levine, An electronic time scale for chemistry. Proc. Natl. Acad. Sci. USA 103(May 2), 6793–6798 (2006)

    Google Scholar 

  2. M.F. Kling, M.J.J. Vrakking, Attosecond electron dynamics. Ann. Rev. Phys. Chem. 59, 463–492 (2008)

    Article  ADS  Google Scholar 

  3. P.B. Corkum, F. Krausz, Attosecond science. Nat. Phys. 3(6), 381–387 (2007)

    Article  Google Scholar 

  4. F. Krausz, M. Ivanov, Attosecond physics. Rev. Mod. Phys. 81(1), 163–234 (2009)

    Article  ADS  Google Scholar 

  5. F. Lépine, G. Sansone, M.J.J. Vrakking, Molecular applications of attosecond laser pulses. Chem. Phys. Lett. 578, 1–14 (2013)

    Article  ADS  Google Scholar 

  6. M.F. Kling, C. Siedschlag, A.J. Verhoef, J.I. Khan, M. Schultze, T. Uphues, Y. Ni, M. Uiberacker, M. Drescher, F. Krausz, M.J.J. Vrakking, Control of electron localization in molecular dissociation. Science 312(5771), 246–248 (2006)

    Article  ADS  Google Scholar 

  7. G. Sansone, F. Kelkensberg, J.F. Perez-Torres, F. Morales, M.F. Kling, W. Siu, O. Ghafur, P. Johnsson, M. Swoboda, E. Benedetti, F. Ferrari, F. Lepine, J.L. Sanz-Vicario, S. Zherebtsov, I. Znakovskaya, A. L’Huillier, M.Y. Ivanov, M. Nisoli, F. Martin, M.J.J. Vrakking, Electron localization following attosecond molecular photoionization. Nature 465(7299), 763–766 (2010)

    Google Scholar 

  8. S. Haessler, J. Caillat, W. Boutu, C. Giovanetti-Teixeira, T. Ruchon, T. Auguste, Z. Diveki, P. Breger, A. Maquet, B. Carre, R. Taieb, P. Salieres, Attosecond imaging of molecular electronic wavepackets. Nat. Phys. 6(3), 200–206 (2010)

    Article  Google Scholar 

  9. W. Li, A.A. Jaron-Becker, C.W. Hogle, V. Sharma, X. Zhou, A. Becker, H.C. Kapteyn, M.M. Murnane, Visualizing electron rearrangement in space and time during the transition from a molecule to atoms. Proc. Natl. Acad. Sci. U.S.A. 107(47), 20219–20222 (2010)

    Article  ADS  Google Scholar 

  10. P. Ranitovic, C.W. Hogle, P. Rivière, A. Palacios, X.M. Tong, N. Toshima, A. González-Castrillo, L. Martin, F. Martín, M.M. Murnane, H. Kapteyn, Attosecond vacuum UV coherent control of molecular dynamics. Proc. Natl. Acad. Sci. U.S.A. 111(3), 912–917 (2014)

    Article  ADS  Google Scholar 

  11. X. Zhou, P. Ranitovic, C.W. Hogle, J.H.D. Eland, H.C. Kapteyn, M.M. Murnane, Probing and controlling non-Born-Oppenheimer dynamics in highly excited molecular ions. Nat. Phys. 8(3), 232–237 (2012)

    Article  Google Scholar 

  12. C. Neidel, J. Klei, C.H. Yang, A. Rouzée, M.J.J. Vrakking, K. Klünder, M. Miranda, C.L. Arnold, T. Fordell, A. L’Huillier, M. Gisselbrecht, P. Johnsson, M.P. Dinh, E. Suraud, P.G. Reinhard, V. Despré, M.A.L. Marques, F. Lépine, Probing time-dependent molecular dipoles on the attosecond time scale. Phys. Rev. Lett. 111(3), 033001 (2013)

    Article  ADS  Google Scholar 

  13. L. Belshaw, F. Calegari, M.J. Duffy, A. Trabattoni, L. Poletto, M. Nisoli, J.B. Greenwood, Observation of ultrafast charge migration in an amino acid. J. Phys. Chem. Lett. 3(24), 3751–3754 (2012)

    Article  Google Scholar 

  14. F. Calegari, D. Ayuso, A. Trabattoni, L. Belshaw, S. De Camillis, S. Anumula, F. Frassetto, L. Poletto, A. Palacios, P. Decleva, J.B. Greenwood, F. Martín, M. Nisoli, Ultrafast electron dynamics in phenylalanine initiated by attosecond pulses. Science 346(6207), 336–339 (2014)

    Article  ADS  Google Scholar 

  15. R. Weinkauf, P. Schanen, A. Metsala, E.W. Schlag, M. Buergle, H. Kessler, Highly efficient charge transfer in peptide cations in the gas phase: threshold effects and mechanism. J. Phys. Chem. 100, 18567–18585 (1996)

    Article  Google Scholar 

  16. O. Smirnova, Y. Mairesse, S. Patchkovskii, N. Dudovich, D. Villeneuve, P. Corkum, M.Y. Ivanov, High harmonic interferometry of multi-electron dynamics in molecules. Nature 460(7258), 972–977 (2009)

    Article  ADS  Google Scholar 

  17. Y. Mairesse, J. Higuet, N. Dudovich, D. Shafir, B. Fabre, E. Mével, E. Constant, S. Patchkovskii, Z. Walters, M.Y. Ivanov, O. Smirnova, High harmonic spectroscopy of multichannel dynamics in strong-field ionization. Phys. Rev. Lett. 104(21), 213601 (2010)

    Article  ADS  Google Scholar 

  18. P.M. Kraus, B. Mignolet, D. Baykusheva, A. Rupenyan, L. Horný, E.F. Penka, G. Grassi, O.I. Tolstikhin, J. Schneider, F. Jensen, L.B. Madsen, A.D. Bandrauk, F. Remacle, H.J. Wörner, Measurement and laser control of attosecond charge migration in ionized iodoacetylene. Science 350(6262), 790–795 (2015)

    Article  ADS  Google Scholar 

  19. E. Goulielmakis, Z.H. Loh, A. Wirth, R. Santra, N. Rohringer, V.S. Yakovlev, S. Zherebtsov, T. Pfeifer, A.M. Azzeer, M.F. Kling, S.R. Leone, F. Krausz, Real-time observation of valence electron motion. Nature 466(7307), 739–743 (2010)

    Article  ADS  Google Scholar 

  20. M. Holler, F. Schapper, L. Gallmann, U. Keller, Attosecond electron wave-packet interference observed by transient absorption. Phys. Rev. Lett. 106(12) (2011)

    Google Scholar 

  21. P. Hockett, C.Z. Bisgaard, O.J. Clarkin, A. Stolow, Time-resolved imaging of purely valence-electron dynamics during a chemical reaction. Nat. Phys. 7(8), 612–615 (2011)

    Article  Google Scholar 

  22. A.N. Pfeiffer, C. Cirelli, M. Smolarski, U. Keller, Recent attoclock measurements of strong field ionization. Chem. Phys. 414, 84–91 (2013)

    Article  ADS  Google Scholar 

  23. P. Eckle, A.N. Pfeiffer, C. Cirelli, A. Staudte, R. Dörner, H.G. Muller, M. Büttiker, U. Keller, Attosecond ionization and tunneling delay time measurements in helium. Science 322(5907), 1525–1529 (2008)

    Article  ADS  Google Scholar 

  24. H. Li, B. Mignolet, G. Wachter, S. Skruszewicz, S. Zherebtsov, F. Süßmann, A. Kessel, S.A. Trushin, N.G. Kling, M. Kübel, B. Ahn, D. Kim, I. Ben-Itzhak, C.L. Cocke, T. Fennel, J. Tiggesbäumker, K.H. Meiwes-Broer, C. Lemell, J. Burgdörfer, R.D. Levine, F. Remacle, M.F. Kling, Coherent electronic wave packet motion in C60 controlled by the waveform and polarization of few-cycle laser fields. Phys. Rev. Lett. 114(12), 123004 (2015)

    Article  ADS  Google Scholar 

  25. A.D. Bandrauk, S. Chelkowski, S. Kawai, H.Z. Lu, Effect of nuclear motion on molecular high-order harmonics and on generation of attosecond pulses in intense laser pulses. Phys. Rev. Lett. 101(15), 153901 (2008)

    Article  ADS  Google Scholar 

  26. J. Caillat, J. Zanghellini, M. Kitzler, O. Koch, W. Kreuzer, A. Scrinzi, Correlated multielectron systems in strong laser fields: a multiconfiguration time-dependent Hartree-Fock approach. Phys. Rev. A 71(1), 012712 (2005)

    Article  ADS  Google Scholar 

  27. M. Nest, T. Klamroth, P. Saalfrank, The multiconfiguration time-dependent Hartree-Fock method for quantum chemical calculations. J. Chem. Phys. 122(12), 124102 (2005)

    Article  ADS  Google Scholar 

  28. I. Burghardt, H.D. Meyer, L.S. Cederbaum, Approaches to the approximate treatment of complex molecular systems by the multiconfiguration time-dependent Hartree method. J. Chem. Phys. 111(7), 2927–2939 (1999)

    Article  ADS  Google Scholar 

  29. J. Jornet-Somoza, B. Lasorne, M.A. Robb, H.D. Meyer, D. Lauvergnat, F. Gatti, A generalised 17-state vibronic-coupling Hamiltonian model for ethylene. J. Chem. Phys. 137(8), 084304 (2012)

    Article  ADS  Google Scholar 

  30. H.D. Meyer, U. Manthe, L.S. Cederbaum, The multi-configurational time-dependent Hartree approach. Chem. Phys. Lett. 165(1), 73–78 (1990)

    Article  ADS  Google Scholar 

  31. P. Alicia, G.-C. Alberto, B. Henri, M. Fernando, Wave packet dynamics in molecular excited electronic states. J. Phys: Conf. Ser. 488(1), 012017 (2014)

    Google Scholar 

  32. Y. Ide, T. Kato, K. Yamanouchi, Non-Born–Oppenheimer molecular wave functions of H2 by extended multi-configuration time-dependent Hartree-Fock method. Chem. Phys. Lett. 595–596, 180–184 (2014)

    Article  Google Scholar 

  33. T. Kato, H. Kono, Time-dependent multiconfiguration theory for ultrafast electronic dynamics of molecules in an intense laser field: electron correlation and energy redistribution among natural orbitals. Chem. Phys. 366(1–3), 46–53 (2009)

    Article  ADS  Google Scholar 

  34. H. Kono, Y. Sato, N. Tanak, T. Kato, K. Nakai, S. Koseki, Y. Fujimura, Quantum mechanical study of electronic and nuclear dynamics of molecules in intense laser fields. Chem. Phys. 304, 203–226 (2004)

    Article  ADS  Google Scholar 

  35. J. Ajay, J. Šmydke, F. Remacle, R.D. Levine, Probing in space and time the nuclear motion driven by nonequilibrium electronic dynamics in ultrafast pumped N2. J. Phys. Chem. A (2016)

    Google Scholar 

  36. B.H. Muskatel, F. Remacle, R.D. Levine, Ultrafast predissociation mechanism of the 1Πu states of 14N2 and its isotopomers upon attosecond excitation from the ground state. J. Phys. Chem. A 116(46), 11311–11318 (2012)

    Article  Google Scholar 

  37. D. Kosloff, R. Kosloff, A Fourier method solution for the time dependent Schrödinger equation as a tool in molecular dynamics. J. Comp. Phys. 52, 35–53 (1983)

    Article  ADS  MATH  Google Scholar 

  38. R. Kosloff, Propagation methods for quantum molecular dynamics. Ann. Rev. Phys. Chem. 45, 145–178 (1994)

    Article  ADS  Google Scholar 

  39. C. Leforestier, R.H. Bisseling, C. Cerjan, M.D. Feit, R. Friesner, A. Guldberg, A. Hammerich, G. Jolicard, W. Karrlein, H.D. Meyer, N. Lipkin, O. Roncero, R. Kosloff, A comparison of different propagation schemes for the time dependent Schrödinger equation. J. Comp. Phys. 94(1), 59–80 (1991)

    Article  ADS  MATH  Google Scholar 

  40. D.J. Tannor, Introduction to Quantum Mechanics. A Time-Dependent Perspective (University Science Book, Sausalito, 2007)

    Google Scholar 

  41. C.P. Koch, R. Kosloff, Correlation dynamics after short-pulse photoassociation. Phys. Rev. A 81(6), 063426 (2010)

    Article  ADS  Google Scholar 

  42. A. Nikodem, R.D. Levine, F. Remacle, Quantum nuclear dynamics pumped and probed by ultrafast polarization controlled steering of a coherent electronic state in LiH. J. Phys. Chem. A (2016)

    Google Scholar 

  43. M. Nest, F. Remacle, R.D. Levine, Pump and probe ultrafast electron dynamics in LiH: a computational study. New J. Phys. 10, 025019–025024 (2008)

    Article  ADS  Google Scholar 

  44. F. Remacle, M. Nest, R.D. Levine, Laser steered ultrafast quantum dynamics of electrons in LiH. Phys. Rev. Lett. 99(18), 183902 (2007)

    Article  ADS  Google Scholar 

  45. I.S. Ulusoy, M. Nest, The multi-configuration electron-nuclear dynamics method applied to LiH. J. Chem. Phys. 136(5), 054112 (2012)

    Article  ADS  Google Scholar 

  46. I.S. Ulusoy, M. Nest, Remarks on the validity of the fixed nuclei approximation in quantum electron dynamics. J. Phys. Chem. A 116(46), 11107–11110 (2012)

    Article  Google Scholar 

  47. Y. Arasaki, K. Takatsuka, Pulse-train photoelectron spectroscopy of electronic and nuclear dynamics in molecules. ChemPhysChem 14(7), 1387–1396 (2013)

    Article  Google Scholar 

  48. J.E. Bækhøj, L. Yue, L.B. Madsen, Nuclear-motion effects in attosecond transient-absorption spectroscopy of molecules. Phys. Rev. A 91(4), 043408 (2015)

    Article  ADS  Google Scholar 

  49. L. Seidner, G. Stock, W. Domcke, Nonperturbative approach to femtosecond spectroscopy: general theory and application to multidimensional nonadiabatic photoisomerization processes. J. Chem. Phys. 103(10), 3998–4011 (1995)

    Article  ADS  Google Scholar 

  50. M.B. Gaarde, C. Buth, J.L. Tate, K.J. Schafer, Transient absorption and reshaping of ultrafast XUV light by laser-dressed helium. Phys. Rev. A 83(1), 013419 (2011)

    Article  ADS  Google Scholar 

  51. H.-J. Werner, P.J. Knowles, F.R. Manby, M. Schuetz, P. Celani, G. Knizia, T. Korona, R. Lindh, A. Mitrushenkov, G. Rauhut, T.B. Adler, R.D. Amos, A. Bernhardsson, A. Berning, D.L. Cooper, M.J.O. Deegan, A.J. Dobbyn, F. Eckert, E. Goll, C. Hampel, A. Hesselmann, G. Hetzer, T. Hrenar, G. Jansen, C. Koeppl, Y. Liu, A.W. Lloyd, R.A. Mata, A.J. May, S.J. McNicholas, W. Meyer, M.E. Mura, A. Nicklass, P. Palmieri, K. Pflueger, R. Pitzer, M. Reiher, T. Shiozaki, H. Stoll, A.J. Stone, R. Tarroni, T. Thorsteinsson, M. Wang, A. Wolf, MOLPRO a package of ab initio programs (2012)

    Google Scholar 

  52. H.J. Werner, P.J. Knowles, A second order multiconfiguration SCF procedure with optimum convergence. J. Chem. Phys. 82(11), 5053–5063 (1985)

    Article  ADS  Google Scholar 

  53. P.J. Knowles, H.-J. Werner, An efficient second-order MC SCF method for long configuration expansions. Chem. Phys. Lett. 115(3), 259–267 (1985)

    Article  ADS  Google Scholar 

  54. H.J. Werner, P.J. Knowles, An efficient internally contracted multiconfiguration–reference configuration interaction method. J. Chem. Phys. 89(9), 5803–5814 (1988)

    Article  ADS  Google Scholar 

  55. P.J. Knowles, H.-J. Werner, An efficient method for the evaluation of coupling coefficients in configuration interaction calculations. Chem. Phys. Lett. 145(6), 514–522 (1988)

    Article  ADS  Google Scholar 

  56. P. Dierckx, Curve and Surface Fitting with Splines. Monographs on Numerical Analysis (Oxford University Press, Oxford, 1993)

    MATH  Google Scholar 

  57. F.X. Gadea, Accurate ab initio calculations for LiH and its ions, LiH+ and LiH. Theor. Chem. Acc. 116(4–5), 566–575 (2006)

    Article  Google Scholar 

  58. F. Remacle, R. Kienberger, F. Krausz, R.D. Levine, On the feasibility of an ultrafast purely electronic reorganization in lithium hydride. Chem. Phys. 338, 342–347 (2007)

    Article  ADS  Google Scholar 

  59. O. Ghafur, A. Rouzee, A. Gijsbertsen, W.K. Siu, S. Stolte, M.J.J. Vrakking, Impulsive orientation and alignment of quantum-state-selected NO molecules. Nat. Phys. 5(4), 289–293 (2009)

    Article  Google Scholar 

  60. L. Holmegaard, J.H. Nielsen, I. Nevo, H. Stapelfeldt, F. Filsinger, J. Kupper, G. Meijer, Laser-induced alignment and orientation of quantum-state-selected large molecules. Phys. Rev. Lett. 102(2), 023001 (2009)

    Article  ADS  Google Scholar 

  61. P.M. Kraus, A. Rupenyan, H.J. Wörner, High-harmonic spectroscopy of oriented OCS molecules: emission of even and odd harmonics. Phys. Rev. Lett. 109(23), 233903 (2012)

    Article  ADS  Google Scholar 

  62. D. Simah, B. Hartke, H.-J. Werner, Photodissociation dynamics of H2S on new coupled ab initio potential energy surfaces. J. Chem. Phys. 111(10), 4523–4534 (1999)

    Article  ADS  Google Scholar 

  63. H.J. Werner, B. Follmeg, M.H. Alexander, Adiabatic and diabatic potential energy surfaces for collisions of CN(X 2Σ+, A 2Π) with He. J. Chem. Phys. 89(5), 3139–3151 (1988)

    Article  ADS  Google Scholar 

  64. H.J. Werner, W. Meyer, MCSCF study of the avoided curve crossing of the two lowest 1Σ+ states of LiF. J. Chem. Phys. 74(10), 5802–5807 (1981)

    Article  ADS  Google Scholar 

  65. M. Baer, The electronic adiabatic-to-diabatic transformation matrix and the Wigner rotation matrix. Chem. Phys. Lett. 347(1–3), 149–156 (2001)

    Article  ADS  Google Scholar 

  66. R. Kosloff, Time-dependent quantum-mechanical methods for molecular dynamics. J. Phys. Chem. 92(8), 2087–2100 (1988)

    Article  Google Scholar 

  67. T. Bredtmann, S. Chelkowski, A.D. Bandrauk, Effect of nuclear motion on molecular high order harmonic pump probe spectroscopy. J. Phys. Chem. A 116(46), 11398–11405 (2012)

    Article  Google Scholar 

  68. A.R. Beck, D.M. Neumark, S.R. Leone, Probing ultrafast dynamics with attosecond transient absorption. Chem. Phys. Lett. 624, 119–130 (2015)

    Article  ADS  Google Scholar 

  69. A.R. Beck, B. Bernhardt, E.R. Warrick, M. Wu, S. Chen, M.B. Gaarde, K.J. Schafer, D.M. Neumark, S.R. Leone, Attosecond transient absorption probing of electronic superpositions of bound states in neon: detection of quantum beats. N. J. Phys. 16(11), 113016 (2014)

    Article  Google Scholar 

  70. P. Nuernberger, S. Ruetzel, T. Brixner, Multidimensional electronic spectroscopy of photochemical reactions. Angew. Chem. Int. Ed. 54(39), 11368–11386 (2015)

    Article  Google Scholar 

  71. T.A.A. Oliver, G.R. Fleming, Following coupled electronic-nuclear motion through conical intersections in the ultrafast relaxation of β-Apo-8′-carotenal. J. Phys. Chem. B 119(34), 11428–11441 (2015)

    Article  Google Scholar 

  72. P.J.M. Johnson, A. Halpin, T. Morizumi, V.I. Prokhorenko, O.P. Ernst, R.J.D. Miller, Local vibrational coherences drive the primary photochemistry of vision. Nat. Chem. 7(12), 980–986 (2015)

    Article  Google Scholar 

  73. B.H. Muskatel, F. Remacle, R.D. Levine, AttoPhotoChemistry. Probing ultrafast electron dynamics by the induced nuclear motion: the prompt and delayed predissociation of N2. Chem. Phys. Lett. 601, 45–48 (2014)

    Article  ADS  Google Scholar 

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Acknowledgements

This work is supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES) under Award #DE-SC0012628. We benefited from our participation in the COST action CM1204 XLIC. FR is a director of research with FNRS (Fonds National de la Recherche Scientifique), Belgium.

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Authors and Affiliations

  1. Département de Chimie, B6c, Université de Liège, B4000, Liège, Belgium

    Astrid Nikodem & F. Remacle

  2. The Fritz Haber Center for Molecular Dynamics and Institute of Chemistry, The Hebrew University of Jerusalem, 91904, Jerusalem, Israel

    R. D. Levine & F. Remacle

  3. Crump Institute for Molecular Imaging and Department of Molecular and Medical Pharmacology, David Geffen School of Medicine and Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, 90095, USA

    R. D. Levine

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  1. Astrid Nikodem
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  2. R. D. Levine
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  3. F. Remacle
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Correspondence to F. Remacle .

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Editors and Affiliations

  1. Department of Chemistry, The University of Tokyo, Tokyo, Japan

    Kaoru Yamanouchi

  2. University of Maryland, College Park, College Park, Maryland, USA

    Wendell T. Hill III

  3. Institute of Optics and Quantum Electronics, Friedrich Schiller University Jena, Jena, Thüringen, Germany

    Gerhard G. Paulus

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Nikodem, A., Levine, R.D., Remacle, F. (2017). Controlling Coherent Quantum Nuclear Dynamics in LiH by Ultra Short IR Atto Pulses. In: Yamanouchi, K., Hill III, W., Paulus, G. (eds) Progress in Ultrafast Intense Laser Science XIII. Springer Series in Chemical Physics(). Springer, Cham. https://doi.org/10.1007/978-3-319-64840-8_3

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