A site-selective spectroscopy study of Ag nanoclusters dispersed in oxyfluoride glass hosts has been carried out. The nano- to millisecond, essentially non-exponential, luminescence kinetics of Ag nanoclusters has been detected in the spectral range from 450 to 1000 nm, when excited at discrete wavelengths in the range 250 to 450 nm. Based on these experimental observations, the energy level configuration coordinate diagram for the involved ground and excited singlet/triplet states of the Ag nanoclusters has been proposed and confirmed by the density functional theory (DFT). The sites for the Ag nanoclusters are argued to be multiple. The structure/geometry of the involved Ag nanoclusters has been suggested to involve spin-paired dimers Ag²⁺, or tetramers Ag₄²⁺, with a varying elongation/distortion along the tetramer diagonals.

© 2012 OSA

1. L. Konig, I. Rabin, W. Schulze, and G. Ertl, “Chemiluminescence in the agglomeration of metal clusters,” Science274(5291), 1353–1355 (1996). [CrossRef] [PubMed]
2. I. Díez and R. H. A. Ras, “Fluorescent silver nanoclusters,” Nanoscale3(5), 1963–1970 (2011). [CrossRef] [PubMed]
3. Z. Shen, H. Duan, and H. Frey, “Water-soluble fluorescent Ag nanoclusters obtained from multiarm star poly(akrilic) acid as molecular hydrogel templates,” Adv. Mater.19(3), 349–352 (2007). [CrossRef]
4. I. Díez, M. Pusa, S. Kulmala, H. Jiang, A. Walther, A. S. Goldmann, A. H. E. Müller, O. Ikkala, and R. H. A. Ras, “Color tuneability and electrochemiluminescence of silver nanoclusters,” Angew. Chem. Int. Ed.48(12), 2122–2125 (2009). [CrossRef]
5. V. K. Tikhomirov, V. D. Rodríguez, A. Kuznetsov, D. Kirilenko, G. Van Tendeloo, and V. V. Moshchalkov, “Preparation and luminescence of bulk oxyfluoride glasses doped with Ag nanoclusters,” Opt. Express18(21), 22032–22040 (2010). [CrossRef] [PubMed]
6. A. S. Kuznetsov, N. T. Cuong, V. K. Tikhomirov, M. Jivanescu, A. Stesmans, L. F. Chibotaru, J. J. Velázquez, V. D. Rodríguez, D. Kirilenko, G. Van Tendeloo, and V. V. Moshchalkov, “Effect of heat-treatment on luminescence and structure of Ag nanoclusters doped oxyfluoride glasses and implication for fiber drawing,” Opt. Mater.34(4), 616–621 (2012). [CrossRef]
7. V. D. Rodríguez, V. K. Tikhomirov, J. Mendez-Ramos, A. C. Yanes, and V. V. Moshchalkov, “Towards broad range and highly efficient down-conversion of solar spectrum by Er3+-Yb3+ co-doped nano-structured glass-ceramics,” Sol. Energy Mater. Sol. Cells94(10), 1612–1617 (2010). [CrossRef]
8. V. K. Tikhomirov, D. Furniss, A. B. Seddon, I. M. Reaney, M. Beggiora, M. Ferrari, M. Montagna, and R. Rolli, “Fabrication and characterization of nanoscale, Er3+-doped, ultratransparent oxyfluoride glass-ceramics,” Appl. Phys. Lett.81(11), 1937–1939 (2002). [CrossRef]
9. V. K. Tikhomirov, T. Vosch, E. Fron, V. D. Rodríguez, J. J. Velázquez, D. Kirilenko, G. Van Tendeloo, J. Hofkens, M. Van der Auweraer, and V. V. Moshchalkov, “Luminescence of oxyfluoride glasses co-doped with Ag nanoclusters and Yb3+ ions,” RCS Adv.2(4), 1496–1501 (2012).
10. A. C. Yanes, J. Del Castillo, M. Torres, J. Peraza, V. D. Rodríguez, and J. Méndez-Ramos, “Nanocrystal-size selective spectroscopy in SnO2: Eu3+ semiconductor quantum dots,” Appl. Phys. Lett.85(12), 2343–2345 (2004). [CrossRef]
11. W. Chen, A. G. Joly, and J. Roark, “Photostimulated luminescence and dynamics of AgI and Ag nanoclusters in zeolites,” Phys. Rev. B65(24), 245404 (2002). [CrossRef]
12. D. A. McQuarrie and J. D. Simon, Physical Chemistry, a Molecular Approach (University Science Books, Sausalito, CA, 1997).
13. M. T. Colvin, A. L. Smeigh, E. M. Giacobbe, S. M. M. Conron, A. B. Ricks, and M. R. Wasielewski, “Ultrafast intersystem crossing and spin dynamics of zinc meso-tetraphenylporphyrin covalently bound to stable radicals,” J. Phys. Chem. A115(26), 7538–7549 (2011). [CrossRef] [PubMed]
14. L. Maretti, P. S. Billone, Y. Liu, and J. C. Scaiano, “Facile photochemical synthesis and characterization of highly fluorescent silver nanoparticles,” J. Am. Chem. Soc.131(39), 13972–13980 (2009). [CrossRef] [PubMed]
15. I. Rabin, W. Schulze, and G. J. Ertl, “Light emission during the agglomeration of silver clusters in noble gas matrices,” J. Chem. Phys.108(12), 5137–5142 (1998). [CrossRef]
16. S. Hull, “Superionics: crystal structures and conduction processes,” Rep. Prog. Phys.67(7), 1233–1314 (2004). [CrossRef]
17. A. Stesmans, “Structural relaxation of Pb defects at the (111)Si/SiO2 interface as a function of oxidation temperature: The Pb-generation-stress relationship,” Phys. Rev. B Condens. Matter48(4), 2418–2435 (1993). [CrossRef] [PubMed]
18. N. T. Cuong, V. K. Tikhomirov, L. F. Chibotaru, A. Stesmans, V. D. Rodríguez, M. T. Nguyen, and V. V. Moshchalkov, “Experiment and theoretical modeling of the luminescence of silver nanoclusters dispersed in oxyfluoride glass,” J. Chem. Phys. (to be published).
19. V. K. Tikhomirov, A. B. Seddon, M. Ferrari, M. Montagna, L. F. Santos, and R. M. Almeida, “The structure of Er3+-doped oxy-fluoride transparent glass-ceramics studied by Raman scattering,” Europhys. Lett.64(4), 529–535 (2003). [CrossRef]
20. S. R. Elliott, “Medium-range structural order in covalent amorphous solids,” Nature354(6353), 445–452 (1991). [CrossRef]
21. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian 09, Revision A.02 (Gaussian, Inc., Wallingford CT, 2009).
22. P. J. Hay and W. R. Wadt, “Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg,” J. Chem. Phys.82(1), 270–283 (1985). [CrossRef]
23. J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized gradient approximation made simple,” Phys. Rev. Lett.77(18), 3865–3868 (1996). [CrossRef] [PubMed]
24. R. Bauernschmitt and R. Ahlrichs, “Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory,” Chem. Phys. Lett.256(4-5), 454–464 (1996). [CrossRef]
25. K. Driesen, V. K. Tikhomirov, C. Gorller-Walrand, V. D. Rodriguez, and A. B. Seddon, “Transparent Ho3+-doped nano-glass-ceramics for efficient infrared emission,” Appl. Phys. Lett.88(7), 073111 (2006). [CrossRef]
26. M. Nirmal, B. O. Dabbousi, M. G. Bawendi, J. J. Macklin, J. K. Trautman, T. D. Harris, and L. E. Brus, “Fluorescence intermittency in single cadmium selenide nanocrystals,” Nature383(6603), 802–804 (1996). [CrossRef]
27. P. Frantsuzov, M. Kuno, B. Janko, and R. A. Marcus, “Universal emission intermittency in quantum dots, nanorods, and nanowires,” Nat. Phys.4(5), 519–522 (2008). [CrossRef]
28. J. Tang and R. A. Marcus, “Mechanisms of fluorescence blinking in semiconductor nanocrystal quantum dots,” J. Chem. Phys.123(5), 054704 (2005). [CrossRef] [PubMed]

Adv. Mater.

• Z. Shen, H. Duan, and H. Frey, “Water-soluble fluorescent Ag nanoclusters obtained from multiarm star poly(akrilic) acid as molecular hydrogel templates,” Adv. Mater.19(3), 349–352 (2007). [CrossRef]

Angew. Chem. Int. Ed.

• I. Díez, M. Pusa, S. Kulmala, H. Jiang, A. Walther, A. S. Goldmann, A. H. E. Müller, O. Ikkala, and R. H. A. Ras, “Color tuneability and electrochemiluminescence of silver nanoclusters,” Angew. Chem. Int. Ed.48(12), 2122–2125 (2009). [CrossRef]

Appl. Phys. Lett.

• V. K. Tikhomirov, D. Furniss, A. B. Seddon, I. M. Reaney, M. Beggiora, M. Ferrari, M. Montagna, and R. Rolli, “Fabrication and characterization of nanoscale, Er3+-doped, ultratransparent oxyfluoride glass-ceramics,” Appl. Phys. Lett.81(11), 1937–1939 (2002). [CrossRef]
• A. C. Yanes, J. Del Castillo, M. Torres, J. Peraza, V. D. Rodríguez, and J. Méndez-Ramos, “Nanocrystal-size selective spectroscopy in SnO2: Eu3+ semiconductor quantum dots,” Appl. Phys. Lett.85(12), 2343–2345 (2004). [CrossRef]
• K. Driesen, V. K. Tikhomirov, C. Gorller-Walrand, V. D. Rodriguez, and A. B. Seddon, “Transparent Ho3+-doped nano-glass-ceramics for efficient infrared emission,” Appl. Phys. Lett.88(7), 073111 (2006). [CrossRef]

Chem. Phys. Lett.

• R. Bauernschmitt and R. Ahlrichs, “Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory,” Chem. Phys. Lett.256(4-5), 454–464 (1996). [CrossRef]

Europhys. Lett.

• V. K. Tikhomirov, A. B. Seddon, M. Ferrari, M. Montagna, L. F. Santos, and R. M. Almeida, “The structure of Er3+-doped oxy-fluoride transparent glass-ceramics studied by Raman scattering,” Europhys. Lett.64(4), 529–535 (2003). [CrossRef]

J. Am. Chem. Soc.

• L. Maretti, P. S. Billone, Y. Liu, and J. C. Scaiano, “Facile photochemical synthesis and characterization of highly fluorescent silver nanoparticles,” J. Am. Chem. Soc.131(39), 13972–13980 (2009). [CrossRef] [PubMed]

J. Chem. Phys.

• I. Rabin, W. Schulze, and G. J. Ertl, “Light emission during the agglomeration of silver clusters in noble gas matrices,” J. Chem. Phys.108(12), 5137–5142 (1998). [CrossRef]
• N. T. Cuong, V. K. Tikhomirov, L. F. Chibotaru, A. Stesmans, V. D. Rodríguez, M. T. Nguyen, and V. V. Moshchalkov, “Experiment and theoretical modeling of the luminescence of silver nanoclusters dispersed in oxyfluoride glass,” J. Chem. Phys. (to be published).
• P. J. Hay and W. R. Wadt, “Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg,” J. Chem. Phys.82(1), 270–283 (1985). [CrossRef]
• J. Tang and R. A. Marcus, “Mechanisms of fluorescence blinking in semiconductor nanocrystal quantum dots,” J. Chem. Phys.123(5), 054704 (2005). [CrossRef] [PubMed]

J. Phys. Chem. A

• M. T. Colvin, A. L. Smeigh, E. M. Giacobbe, S. M. M. Conron, A. B. Ricks, and M. R. Wasielewski, “Ultrafast intersystem crossing and spin dynamics of zinc meso-tetraphenylporphyrin covalently bound to stable radicals,” J. Phys. Chem. A115(26), 7538–7549 (2011). [CrossRef] [PubMed]

Nanoscale

• I. Díez and R. H. A. Ras, “Fluorescent silver nanoclusters,” Nanoscale3(5), 1963–1970 (2011). [CrossRef] [PubMed]

Nat. Phys.

• P. Frantsuzov, M. Kuno, B. Janko, and R. A. Marcus, “Universal emission intermittency in quantum dots, nanorods, and nanowires,” Nat. Phys.4(5), 519–522 (2008). [CrossRef]

Nature

• M. Nirmal, B. O. Dabbousi, M. G. Bawendi, J. J. Macklin, J. K. Trautman, T. D. Harris, and L. E. Brus, “Fluorescence intermittency in single cadmium selenide nanocrystals,” Nature383(6603), 802–804 (1996). [CrossRef]
• S. R. Elliott, “Medium-range structural order in covalent amorphous solids,” Nature354(6353), 445–452 (1991). [CrossRef]

Opt. Express

• V. K. Tikhomirov, V. D. Rodríguez, A. Kuznetsov, D. Kirilenko, G. Van Tendeloo, and V. V. Moshchalkov, “Preparation and luminescence of bulk oxyfluoride glasses doped with Ag nanoclusters,” Opt. Express18(21), 22032–22040 (2010). [CrossRef] [PubMed]

Opt. Mater.

• A. S. Kuznetsov, N. T. Cuong, V. K. Tikhomirov, M. Jivanescu, A. Stesmans, L. F. Chibotaru, J. J. Velázquez, V. D. Rodríguez, D. Kirilenko, G. Van Tendeloo, and V. V. Moshchalkov, “Effect of heat-treatment on luminescence and structure of Ag nanoclusters doped oxyfluoride glasses and implication for fiber drawing,” Opt. Mater.34(4), 616–621 (2012). [CrossRef]

Phys. Rev. B

• W. Chen, A. G. Joly, and J. Roark, “Photostimulated luminescence and dynamics of AgI and Ag nanoclusters in zeolites,” Phys. Rev. B65(24), 245404 (2002). [CrossRef]

Phys. Rev. B Condens. Matter

• A. Stesmans, “Structural relaxation of Pb defects at the (111)Si/SiO2 interface as a function of oxidation temperature: The Pb-generation-stress relationship,” Phys. Rev. B Condens. Matter48(4), 2418–2435 (1993). [CrossRef] [PubMed]

Phys. Rev. Lett.

• J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized gradient approximation made simple,” Phys. Rev. Lett.77(18), 3865–3868 (1996). [CrossRef] [PubMed]

RCS Adv.

• V. K. Tikhomirov, T. Vosch, E. Fron, V. D. Rodríguez, J. J. Velázquez, D. Kirilenko, G. Van Tendeloo, J. Hofkens, M. Van der Auweraer, and V. V. Moshchalkov, “Luminescence of oxyfluoride glasses co-doped with Ag nanoclusters and Yb3+ ions,” RCS Adv.2(4), 1496–1501 (2012).

Rep. Prog. Phys.

• S. Hull, “Superionics: crystal structures and conduction processes,” Rep. Prog. Phys.67(7), 1233–1314 (2004). [CrossRef]

Science

• L. Konig, I. Rabin, W. Schulze, and G. Ertl, “Chemiluminescence in the agglomeration of metal clusters,” Science274(5291), 1353–1355 (1996). [CrossRef] [PubMed]

Sol. Energy Mater. Sol. Cells

• V. D. Rodríguez, V. K. Tikhomirov, J. Mendez-Ramos, A. C. Yanes, and V. V. Moshchalkov, “Towards broad range and highly efficient down-conversion of solar spectrum by Er3+-Yb3+ co-doped nano-structured glass-ceramics,” Sol. Energy Mater. Sol. Cells94(10), 1612–1617 (2010). [CrossRef]

Other

• D. A. McQuarrie and J. D. Simon, Physical Chemistry, a Molecular Approach (University Science Books, Sausalito, CA, 1997).
• M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian 09, Revision A.02 (Gaussian, Inc., Wallingford CT, 2009).

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