Hyperfine Interactions

, Volume 175, Issue 1–3, pp 141–150 | Cite as

Mössbauer, nuclear inelastic scattering and density functional studies on the second metastable state of Na2[Fe(CN)5NO]·2H2O

  • V. Rusanov
  • H. Paulsen
  • L. H. Böttger
  • H. Winkler
  • J. A. Wolny
  • N. Koop
  • Th. Dorn
  • C. Janiak
  • A. X. Trautwein


The structure of the light-induced metastable state SII of Na2[Fe(CN)5NO]·2H2O was investigated by transmission Mössbauer spectroscopy (TMS) in the temperature range between 85 and 135 K, nuclear inelastic scattering (NIS) at 98 K using synchrotron radiation and density functional theory (DFT) calculations. The DFT and TMS results strongly support the view that the NO group in SII takes a side-on molecular orientation and, further, is dynamically displaced from one eclipsed, via a staggered, to a second eclipsed orientation. The population conditions for generating SII are optimal for measurements by TMS, yet they are modest for accumulating NIS spectra. Optimization of population conditions for NIS measurements is discussed and new NIS experiments on SII are proposed.


Density functional calculations Metastable states Mössbauer spectroscopy Nuclear inelastic scattering 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Hauser, U., Oestreich, V., Rohrweck, H.D.: On optical dispersion in transparent molecular systems. Z. Phys. A. 280, 17–25 (1977)CrossRefGoogle Scholar
  2. 2.
    Rusanov, V., Stankov, Sv., Trautwein, A.X.: Photoswitching of nitroprussides. Hyperfine Interact. 144/145, 307–323 (2002)CrossRefADSGoogle Scholar
  3. 3.
    Woike, Th., Kirchner, W., Schetter, G., Barthel, Th., Kim, H., Haussühl, S.: New information storage elements on the basis of metastable electronic states. Opt. Commun. 106, 6–10 (1994)CrossRefADSGoogle Scholar
  4. 4.
    Schaniel, D., Woike, Th., Delley, B., Boskovic, C., Biner, D., Krämer, K.W., Güdel, H.-U.: Long-lived light-induced metastable states in trans-[Ru(NH3)4(H2O)NO]Cl3H2O and related compounds. Phys. Chem. Chem. Phys. 7, 1164–1170 (2005)CrossRefGoogle Scholar
  5. 5.
    Rüdlinger, M., Schefer, J., Chevrier, G., Furer, N., Güdel, H.-U., Haussühl, S., Heger, G., Schweiss, P., Vogt, T., Woike, T., Zöllner, H.: Light-induced structural changes in sodiumnitroprusside (Na2(Fe(CN)5NO)·2D2O) at 80 K. Z. Phys. B. 83, 125–130 (1991)CrossRefGoogle Scholar
  6. 6.
    Schefer, J., Woike, Th., Imlau, M., Delley, B.: Possible reaction coordinates in the metastable states of sodiumnitro-prusside Na2[Fe(CN)5NO]·2H2O: a discussion based on neutron diffraction- and spectroscopic measurements. Eur. Phys. J. B. 3, 349 (1998)CrossRefADSGoogle Scholar
  7. 7.
    Schaniel, D., Schefer, J., Imlau, M., Woike, Th.: Light-induced structural changes by excitation of metastable states in Na2[Fe(CN)5NO]×2H2O single crystals. Phys. Rev. B. 68, 104108 (2003)CrossRefADSGoogle Scholar
  8. 8.
    Schefer, J., Woike, Th., Haussühl, S., Fernandez Diaz, M.D.: Z. Kristallogr. 212, 29 (1997)Google Scholar
  9. 9.
    Güdel, H.-U.: Comment on the nature of the light-induced metastable states in nitroprussides. Chem. Phys. Lett. 175, 262–266 (1990)CrossRefADSGoogle Scholar
  10. 10.
    Carducci, M.D., Pressprich, M.R., Coppens, P.: Light-induced structural changes by excitation of metastable states in Na2[Fe(CN)5NO]×2H2O single crystals. J. Am. Chem. Soc. 119, 2669–2678 (1997)CrossRefGoogle Scholar
  11. 11.
    Delley, B., Schefer, J., Woike, Th.: Giant lifetimes of optically excited states and the elusive structure of sodiumnitroprusside. J. Chem. Phys. 107, 10067–10074 (1997)CrossRefADSGoogle Scholar
  12. 12.
    Blaha, P., Schwarz, K., Faber, W., Luitz, J.: Calculation of electric field gradients in solids: how theory can complement experiment. Hyperfine Interact. 126, 389–395 (2000)CrossRefADSGoogle Scholar
  13. 13.
    Coppens, P., Novozhilova, I., Kovalevsky, A.: Photoinduced linkage isomers of transition—metal nitrosyl compounds and related complexes. Chem. Rev. 102, 861–883 (2002)CrossRefGoogle Scholar
  14. 14.
    Morioka, Y., Takeda, S., Tomizawa, H., Miki, E.: Molecular vibrations and structure of the light-induced metastable state of [Fe(CN)5NO]2−. Chem. Phys. Lett. 292, 625–630 (1998)CrossRefADSGoogle Scholar
  15. 15.
    Chacón Villalba, M.E., Güida, J.A., Varelti, E.L., Aymonic, P.J.: Infrared evidence of NO linkage photoisomerization in Na2[Fe(CN)5NO]×2H2O at low temperature: experimental and theoretical (DFT) isotopic shifts from 15N(O), 18O and 54Fe species. Spectrochim. Acta, Part A 57, 367–373 (2001)CrossRefGoogle Scholar
  16. 16.
    Rusanov, V., Woike, T., Kim, H., Angelov, V., Bonchev, Ts., Haussühl, S.: Angle-dependent Mössbauer study of the ground and second new metastable state in Na2[Fe(CN)5NO]×2H2O single crystals. Solid State Comm. 126, 457–462 (2003)CrossRefADSGoogle Scholar
  17. 17.
    Woike, Th., Kirchner, W., Kim, H., Haussühl, S., Rusanov, V., Angelov, V., Ormandjiev, S., Bonchev, Ts., Schroeder, A.N.F.: Mössbauer parameters of the two long-lived metastable states in Na2[Fe(CN)5NO]×2H2O single crystals. Hyperfine Interact. 77, 265–275 (1993)CrossRefADSGoogle Scholar
  18. 18.
    Paulsen, H., Winkler, H., Trautwein, A.X., Grünsteudel, H., Rusanov, V., Toftlund, H.: Measurement and simulation of nuclear inelastic-scattering spectra of molecular crystals. Phys. Rev. B. 59, 975–984 (1999)CrossRefADSGoogle Scholar
  19. 19.
    Paulsen, H., Rusanov, V., Benda, R., Herta, C., Schünemann, V., Janiak, C., Dorn, Th., Chumakov, A., Winkler, H., Trautwein, A.X.: Metastable isonitrosyl structure of the nitroprusside anion confirmed by nuclear inelastic scattering. J. Am. Chem. Soc. 124, 3007–3011 (2002)CrossRefGoogle Scholar
  20. 20.
    Chumakov, A., Rüffer, R., Leupold, O., Sergueev, I.: Insight to dynamics of molecules with nuclear inelastic scattering. Struc. Chem. 14, 109–119 (2003)CrossRefGoogle Scholar
  21. 21.
    Seto, M., Yoda, Y., Kikuta, S., Zhang, X.W., Ando, M.: Observation of nuclear resonant scattering accompanied by phonon excitation using synchrotron radiation. Phys. Rev. Lett. 74, 3828–3831 (1995)CrossRefADSGoogle Scholar
  22. 22.
    Sturhahn, W., Toellner, T.S., Alp, E.E., Zhang, X., Ando, M., Yoda, Y., Kikuta, S., Seto, M., Kimball, C.W., Dabrowski, B.: Phonon density of states measured by inelastic nuclear resonant scattering. Phys. Rev. Lett. 74, 3832–3835 (1995)CrossRefADSGoogle Scholar
  23. 23.
    Schaniel, D., Woike, Th., Schefer, J., Petřiček, V.: Structure of the light-induced metastable state SII in Na2[Fe(CN)5NO]×2H2O. Phys. Rev. B. 71, 174112 (2005)CrossRefADSGoogle Scholar
  24. 24.
    Schaniel, D., Woike, Th., Schefer, J., Petřiček, V., Krämer, K.W., Güdel, H.-U.: Neutron diffraction shows a photoinduced isonitrosyl linkage isomer in the metastable state SI of Na2[Fe(CN)5NO]×2D2O. Phys. Rev. B. 73, 174108 (2006)CrossRefADSGoogle Scholar
  25. 25.
    Janiak, C., Dorn, Th., Paulsen, H., Wrackmeyer, B.: Synthesis of isotope enriched (CN3H6)2[57Fe(CN)5NO] starting from 57Fe. Z. Anorg. Allg. Chem. 627, 1663–1668 (2001)CrossRefGoogle Scholar
  26. 26.
    Chumakov, A.I., Rüffer, R.: Nuclear inelastic scattering. Hyperfine Interact. 113, 59–79 (1998)CrossRefADSGoogle Scholar
  27. 27.
    Rüffer, R., Chumakov, A.I.: Nuclear resonance beamline at ESRF. Hyperfine Interact. 97–98, 589–604 (1996)CrossRefGoogle Scholar
  28. 28.
    Becke, A.D.: Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, 5648–5652 (1993)CrossRefADSGoogle Scholar
  29. 29.
    Schaefer, A., Horn, H., Ahlrichs, R.: Fully optimized contracted Gaussian basis sets for atoms Li to Kr. J. Chem. Phys. 97, 2571–2577 (1992)CrossRefADSGoogle Scholar
  30. 30.
    Schaefer, A., Huber, C., Ahlrichs, R.: Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr. J. Chem. Phys. 100, 5829–5835 (1994)CrossRefADSGoogle Scholar
  31. 31.
    Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery, Jr., J.A., Vreven, T., Kudin, K.N., Burant, J.C., Millam, J.M., Iyengar, S.S., Tomasi, J., Barone, V., Mennucci, B., Cossi, M., Scalmani, G., Rega, N., Petersson, G.A., Nakatsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J.E., Hratchian, H.P., Cross, J.B., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Ayala, P.Y., Morokuma, K., Voth, G.A., Salvador, P., Dannenberg, J.J., Zakrzewski, V.G., Dapprich, S., Daniels, A.D., Strain, M.C., Farkas, O., Malick, D.K., Rabuck, A.D., Raghavachari, K., Foresman, J.B., Ortiz, J.V., Cui, Q., Baboul, A.G., Clifford, S., Cioslowski, J., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Martin, R.L., Fox, D.J., Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Challacombe, M., Gill, P.M.W., Johnson, B., Chen, W., Wong, M.W., Gonzalez, C., Pople, J.A., B.01 ed., Gaussian, Inc., Pittsburgh PA, (2003)Google Scholar
  32. 32.
    Peng, C., Ayala, P.Y., Schlegel, H.B., Frisch, M.J.: Using redundant internal coordinates to optimize equilibrium geometries and transition states. J. Comp. Chem. 17, 49–56 (1996)CrossRefGoogle Scholar
  33. 33.
    Peng, C., Schlegel, H.B.: Combining synchronous transit and quasi-newton methods for finding transition states. Isr. J. Chem. 33, 449 (1993)Google Scholar

Copyright information

© Springer Science+Business Media B.V. 2008

Authors and Affiliations

  • V. Rusanov
    • 1
  • H. Paulsen
    • 2
  • L. H. Böttger
    • 2
  • H. Winkler
    • 2
  • J. A. Wolny
    • 2
  • N. Koop
    • 3
  • Th. Dorn
    • 4
  • C. Janiak
    • 4
  • A. X. Trautwein
    • 2
  1. 1.Department of Atomic Physics, Faculty of PhysicsUniversity of SofiaSofiaBulgaria
  2. 2.Institut für PhysikUniversität zu LübeckLübeckGermany
  3. 3.Institut für Biomedizinische OptikUniversität zu LübeckLübeckGermany
  4. 4.Institut für Anorganische und Analytische ChemieUniversität FreiburgFreiburgGermany

Personalised recommendations