Spatio-temporal dynamical systems in inner-shell photoionization in free molecules, clusters, and solids

E. S. Klyushina ; Yu. S. Krivosenko ; A. A. Pavlychev

Contemporary Mathematics. Fundamental Directions, Proceedings of the Sixth International Conference on Differential and Functional-Differential Equations (Moscow, August 14–21, 2011). Part 4, Tome 48 (2013), pp. 61-74.

Résumé

Dynamic spatial hole localization and symmetry breaking phenomena are examined. Absorption of X-ray synchrotron and free-electron-laser radiation in matter is accompanied by strong dynamic corehole localization and temporary trap of the electron ejected from a deep level within the finite size potential barrier. As a result the symmetry of core excited states is reduced in comparison with ground state as the inversion symmetry is being broken. This is a very general property of coreexcited polyatomic compounds with equivalent atoms as their equivalence implies their equal probability of excitation averaged over large timescale but not simultaneous core excitation. Different approaches to rationalizing the symmetry breaking phenomena are presented and discussed with the emphasis on the quasiatomic dynamic corehole localization model. By examining the experimental ultrafast probe of photoabsorption processes we demonstrate an important role of spatio-temporal (nanometric-femtosecond) dynamically localized coreexcited moieties in molecule, clusters and solids. The photoelectron angular distributions from $\mathrm N$ and $\mathrm O$ $1$s levels in fixed-in-space $\mathrm N_2$ and $\mathrm{CO}_2$ molecules, the photoelectron induced rotational heating of $\mathrm N_2$, the Auger decay spectra of $\mathrm N_2$ and the near $\mathrm S$ $1$s edge X-ray absorption fine structure of free $\mathrm{SF}_6$ molecules are discussed in more detail.

Bibliographie

[1] Amusya M. Ya., Atomnyi fotoeffekt, Nauka, M., 1987

[2] Vedrinskii R. V., Kraizman V. L., Novakovich A. A., Teterin Yu. A., Formirovanie osobennostei v rentgenovskikh spektrakh pogloscheniya mnogoatomnykh sistem. Sluchai proizvolnoi simmetrii, Preprint IAE-3368/12, IAE im. Kurchatova, 1980

[3] Landau L. D., Lifshits E. M., Kvantovaya mekhanika: nerelyativistskaya teoriya, Nauka, M., 1974

[4] Adachi J., Hosaka K., Furuya S., Soejima K., Takahashi M., Yagishita A., Semenov S. K., Cherepkov N. A., “Shape-resonance-enhanced vibrational effects in the angular distributions of $C 1s$ photoelectrons from fixed-in-space $CO$ molecules”, Phys. Rev. Lett., 91 (2003), 163001 | DOI

[5] Adachi J., Hosaka K., Teramoto T., Yamazaki M., Watanabe N., Takahashi M., Yagishita A., “Photoelectron-photoion-photoion momentum spectroscopy as a direct probe of the core-hole localization in $C 1s$ photoionization of $C_2H_2$”, J. Phys. B, 40 (2007), F285 | DOI

[6] Bagus P. S., Schaefer H. F., “Localized and delocalized $1s$ hole states of the $O_2^+$ molecular ion”, J. Chem. Phys., 56:1 (1972), 224–226 | DOI

[7] Becker U., Gessner O., Rüdel A., “Photoelectron scattering in molecules and fullerenes”, J. El. Spectroscopy Relat. Phenom., 108:1–3 (2000), 189–201 | DOI

[8] Bethe H. A., Intermediate quantum mechanics, W. A. Benjamin Inc., New York—Amsterdam, 1964 | MR

[9] Cederbaum L. S., Domcke W., “Localized and delocalized core holes and their interrelation”, J. Chem. Phys., 66:11 (1977), 5084–5086 | DOI

[10] Chen C. T., Ma Y., Sette F., “$K$-shell photoabsorption of the $N_2$ molecule”, Phys. Rev. A, 40 (1989), 6737–6740 | DOI

[11] Domcke W., Cederbaum L. S., “Electronic recoil effects in high-energy photoelectron spectroscopy”, J. El. Spectroscopy Relat. Phenom., 13:3 (1978), 161–173 | DOI

[12] Filatova E. O., Pavlychev A. A., X-ray optics and inner-shell electronics of h-BN, Nova Science Publ. Inc., New York, 2011

[13] Flesch R., Serdaroglu E., Blobner F., Feulner P., Brykalova X. O., Pavlychev A. A., Kosugi N., Rühl E., “Gas-to-solid shift of $C 1s$-excited benzene”, Phys. Chem. Chem. Phys., 14:26 (2012), 9397–9402 | DOI

[14] Flesch R., Serdaroglu E., Klyushina E. S., Blobner F., Feulner P., Brykalova X. O., Pavlychev A. A., Rühl E., v pechati

[15] Hergenhahn U., Kugeler O., Rüdel A., Rennie E. E., Bradshaw A. M., “Symmetry-selective observation of the $N 1s$ shape resonance in $N_2$”, J. Phys. Chem. A., 105 (2001), 5704–5708 | DOI

[16] Hudson E., Shirley D. A., Domke M., Remmers G., Puschmann A., Mandel T., Xue C., Kaindl G., “High-resolution measurements of near-edge resonances in the core-level photoionization spectra of $SF_6$”, Phys. Rev. A, 47:1 (1993), 361–373 | DOI

[17] Kivimäki A., Kempgenns B., Maier K., Köppe H. M., Piancastelli M. N., Neeb M., Bradshaw A. M., “Vibrationally resolved $O 1s$ photoelectron spectrum of $CO_2$: vibronic coupling and dynamic core-hole localization”, Phys. Rev. Lett., 79:6 (1997), 998–1001 | DOI

[18] Kosugi N., “Exchange interaction in core excitation of diatomic systems”, Chem. Phys., 289 (2003), 117–134 | DOI

[19] Kukk E., Thomas T. D., Ueda K., “Recoil effects in molecular photoemission”, J. El. Spectroscopy Relat. Phenom., 183:1–3 (2011), 53–58 | DOI

[20] Kukk E., Ueda K., Hergenhahn U., Liu X.-J., Prümper G., Yoshida H., Tamenori Y., Makochekanwa C., Tanaka T., Kitajima M., Tanaka H., “Violation of the Franck—Condon Principle due to recoil effects in high energy molecular core-level photoionization”, Phys. Rev. Lett., 95 (2005), 133001 | DOI

[21] Mielke A., Roubíček T., “A rate-independent model for inelastic behavior of shape-memory alloys”, Multiscale Model Simul., 1:4 (2003), 571–597 | DOI | MR | Zbl

[22] Pavlychev A. A., Brykalova X. O., Flesch R., Rühl E., “Shape resonances in molecular clusters: the $2t_{2g}$ shape resonances in $S 2p$-excited sulfur hexafluoride clusters”, J. El. Spectroscopy Relat. Phenom., 8:16 (2006), 1914–1921

[23] Pavlychev A. A., Brykalova X. O., Mistrov D. A., Flesch R., Rühl E., “Position and line shape of the $2t_{2g}$-shape resonance in $S 2p$-excited sulfur hexafluoride clusters”, J. El. Spectroscopy Relat. Phenom., 166–167 (2008), 45–52 | DOI

[24] Pavlychev A. A., Fominych N. G., Watanabe N., Soejima K., Shigemasa E., Yagishita A., “Dynamic properties of $N$ and $O 1s^{-1}\sigma_u^*$ shape resonances in $N_2$ and $CO_2$ molecules”, Phys. Rev. Lett., 81:17 (1998), 3623–3626 | DOI

[25] Pavlychev A. A., Mistrov D. A., “Spectral distributions of vibrational excitations accompanying $1s$ shell photoionization in small molecules”, J. Phys. B, 42 (2009), 055103 | DOI

[26] Pavlychev A. A., Rühl E., “Dynamic localization of inner-shell excitations in free atomic and molecular clusters”, J. El. Spectroscopy Relat. Phenom., 106:2–3 (2000), 207–220 | DOI

[27] Piancastelli M. N., Lindle D. W., Ferrett T. A., Shirley D. A., “The relationship between shape resonances and bond lengths”, J. Chem. Phys., 86:5 (1987), 2765–2771 | DOI

[28] Poliakoff E. D., Choi H. C., Rao R. M., Mihill A. G., Kakar S., Wang K., McKoy V., “Photoion rotational distributions from near-threshold to deep in the continuum”, J. Chem. Phys., 103 (1995), 1773–1787 | DOI

[29] Rühl E., Flesch R., “Mechanism of anion formation in $C 1s\to\pi^*$-excited carbon dioxide”, J. Chem. Phys., 121:11 (2004), 5322–5327 | DOI

[30] Schmidbauer M., Kilcoyne A. L. D., Köppe H. M., Feldhaus J., Bradshaw A. M., “Shape resonances and multielectron effects in the core-level photoionization of $CO_2$”, Phys. Rev. A, 52:3 (1995), 2095–2108 | DOI

[31] Schöffler M. S., Titze M. S. J., Petridis N., Jahnke T., Cole K., Schmidt L. Ph. H., Czasch A., Akoury D., Jagutsky O., Williams J. B., Cherepkov N. A., Semenov S. K., McCurdy C. W., Rescigno T. N., Cocke C. L., Osipov T., Lee S., Prior M. H., Belcasem A., Landers A. L., Schmidt-Böcking H., Weber Th., Dörner R., “Ultrafast probing of core hole localization in $N_2$”, Science, 320 (2008), 920–923 | DOI

[32] Scully S. W. J., Mackie R. A., Browning R., Dunn K. F., Latimer C. J., “Negative photoion spectroscopy of $SF_6$ in the inner valence and $S 2p$ energy regions”, J. Phys. B, 35:12 (2002), 2703–2712 | DOI

[33] Takata Y., Kayanuma Y., Yabashi M., Tamasaku K., Nishino Y., Miwa D., Harada Y., Horiba K., Shin S., Tanaka S., Ikenaga E., Kobayashi K., Senba Y., Ohashi H., Ishikawa T., “Recoil effects of photoelectrons in a solid”, Phys. Rev. B, 75 (2007), 233404 | DOI

[34] Thiel A., Schirmer J., Köppel H., “An intermediate state representation approach to $K$-shell ionization in molecules. II. Computational tests”, J. Chem. Phys., 119 (2003), 2088–2101 | DOI

[35] Thomas T. D., Kukk E., Fukuzawa H., Ueda K., Püttner R., Tamenori Y., Asahina T., Kuze N., Kato H., Hoshino M., Tanaka H., Meyer M., Plenge J., Wirsing A., Serdaroglu E., Flesch R., Rühl E., Gavrilyuk S., Gel'mukhanov F., Lindblad A., Saetre L. J., “Photoelectron-recoil-induced rotational excitation of the $B^2\Sigma_u^+$ state in $N_2^+$”, Phys. Rev. A, 79 (2009), 022506 | DOI

[36] Ueda K., “To be or not to be localized”, Science, 320 (2008), 884–885 | DOI

[37] Vinogradov A. S., Fedoseenko S. I., Krasnikov S. A., Preobrajenski A. B., Sivkov V. N., Vyalikh D. V., Molodtsov S. L., Adamchuk V. K., Laubschat C., Kaindl G., “Low-lying unoccupied electronic states in 3d transition-metal fluorides probed by NEXAFS at the $F 1s$ threshold”, Phys. Rev. B, 71 (2005), 045127 | DOI

[38] Vinogradov A. S., Zimkina T. M., “Photoabsorption cross section of $SF_6$ in soft and ultrasoft X-rays”, Opt. Spectrosc. (USSR), 32 (1972), 17–19

[39] Vos M., Went M. R., Kayanuma Y., Takata Y., Mayers J., “Comparison of recoil effects in graphite as observed by photoemission, electron scattering, and neutron scattering”, Phys. Rev. B, 78 (2008), 024301 | DOI

[40] Watanabe N., Adachi J., Soejima K., Shigemasa E., Yagishita A., Fominych N. G., Pavlychev A. A., “Fixed-molecule $1s\sigma_{g,u}$ photoelectron angular distributions as a probe of $\sigma_g^*$ and $\sigma_u^*$ shape resonances of $CO_2$”, Phys. Rev. Lett., 78:26 (1997), 4910–4913 | DOI