Journal of Chemical Physics
Feedback | Help | Exit
The Journal of Chemical Physics
   
 
 
 
Previous Article
A study of the ground and excited states of Al3 and Al<sub>3</sub><sup>-</sup>. I. 488 nm anion photoelectron spectrum
The vibrationally resolved, 488 nm anion photoelectron spectrum of aluminum trimer displays transitions from two electronic states of Al3-" align="middle"/> to four states of Al3. Franck–Condon ...
Next Article
Regular vibrational state progressions at the dissociation limit of SCCl2
We observe sharp features in the vibrational spectrum of SCCl2 at and above its two lowest-lying dissociation limits. Highly regular vibrational progressions persist at dissociation, as in some smalle...

A study of the ground and excited states of Al3 and Al3−. II. Computational analysis of the 488  nm anion photoelectron spectrum and a reconsideration of the Al3 bond dissociation energy

J. Chem. Phys. 130, 024304 (2009); doi:10.1063/1.3008056

Published 12 January 2009

You are not logged in to this journal. Log in

Stephen R. Miller, Nathan E. Schultz, Donald G. Truhlar, and Doreen G. Leopold
Chemistry Department, University of Minnesota, 207 Pleasant Street S.E., Minneapolis, Minnesota 55455, USA
Computational results are reported for the ground and low-lying excited electronic states of Al3− and Al3 and compared with the available spectroscopic data. In agreement with previous assignments, the six photodetachment transitions observed in the vibrationally resolved 488  nm photoelectron spectrum of Al3− are assigned as arising from the ground X-tilde   1A<sub>1</sub><sup>[prime]</sup>(1A1) and excited 3B2 states of Al3− and accessing the ground X-tilde   2A<sub>1</sub><sup>[prime]</sup>(2A1) and excited 2A<sub>2</sub><sup>[double-prime]</sup>(2B1), 4A2, and 2B2 states of Al3 (with C2v labels for D3h states in parentheses). Geometries and vibrational frequencies obtained by PBE0 hybrid density functional calculations using the 6-311+G(3d2f) basis set and energies calculated using coupled cluster theory with single and double excitations and a quasiperturbative treatment of connected triple excitations (CCSD(T)) with the aug-cc-pVxZ {x=D, T, Q} basis sets with exponential extrapolation to the complete basis set limit are in good agreement with experiment. Franck–Condon spectra calculated in the harmonic approximation, using either the Sharp–Rosenstock–Chen method which includes Duschinsky rotation or the parallel-mode Hutchisson method, also agree well with the observed spectra. Possible assignments for the higher-energy bands observed in the previously reported UV photoelectron spectra are suggested. Descriptions of the photodetachment transition between the Al3− and Al3 ground states in terms of natural bond order (NBO) analyses and total electron density difference distributions are discussed. A reinterpretation of the vibrational structure in the resonant two-photon ionization spectrum of Al3 is proposed, which supports its original assignment as arising from the X-tilde   2A<sub>1</sub><sup>[prime]</sup> ground state, giving an Al3 bond dissociation energy, D0(Al2–Al), of 2.403±0.001  eV. With this reduction by 0.3  eV from the currently recommended value, the present calculated dissociation energies of Al3, Al3−, and Al3+ are consistent with the experimental data. ©2009 American Institute of Physics
History: Received 26 July 2008; accepted 7 October 2008; published 12 January 2009
Permalink: http://link.aip.org/link/?JCPSA6/130/024304/1
BUY THIS ARTICLE   (US$28)
Download HTML Download Sectioned HTML Download PDF (718 kB) View Cart

EDITORIALLY RELATED

  1. A study of the ground and excited states of Al3 and Al<sub>3</sub><sup>-</sup>. I. 488 nm anion photoelectron spectrum
    Peter W. Villalta et al.
    J. Chem. Phys. 130, 024303 (2009)

Supplemental Material

KEYWORDS and PACS

Keywords
PACS
  • 33.60.+q
    Photoelectron spectra of molecules
  • 33.15.Ry
    Molecular ionization potentials, electron affinities, molecular core binding energy
  • 31.15.bw
    Coupled-cluster theory
  • 33.20.Tp
    Vibrational analysis (molecular spectra)
  • 33.70.Ca
    Molecular oscillator and band strengths, lifetimes, transition moments, and Franck-Condon factors
  • YEAR: 2009

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (83)
View in Separate Window/Tab
For access to fully linked references, you need to log in. For access to fully linked references, you need to Log in.
  1. A. I. Boldyrev and L.-S. Wang, Chem. Rev. (Washington, D.C.) 105, 3716 (2005).
  2. A. E. Kuznetsov, A. I. Boldyrev, H.-J. Zhai, X. Li, and L.-S. Wang, J. Am. Chem. Soc. 124, 11791 (2002);
  3. Figure 6, MO pictures.
  4. A. E. Kuznetsov and A. I. Boldyrev, Struct. Chem. 13, 141 (2002).
  5. C.-G. Zhan, F. Zheng, and D. A. Dixon, J. Am. Chem. Soc. 124, 14795 (2002).
  6. K. K. Baeck and R. J. Bartlett, J. Chem. Phys. 109, 1334 (1998).
  7. D. E. Woon and T. H. Dunning, Jr., J. Chem. Phys. 101, 8877 (1994).
  8. J. S. Tse, J. Chem. Phys. 92, 2488 (1990).
  9. K. K. Sunil and K. D. Jordan, J. Phys. Chem. 92, 2774 (1988).
  10. J. S. Tse, J. Mol. Struct. 165, 21 (1988).
  11. G. Pacchioni, P. Fantucci, and J. Koutecky, Chem. Phys. Lett. 142, 85 (1987).
  12. C. W. Bauschlicher, Jr., H. Partridge, S. R. Langhoff, P. R. Taylor, and S. P. Walch, J. Chem. Phys. 86, 7007 (1987).
  13. H. Basch, Chem. Phys. Lett. 136, 289 (1987).
  14. L. G. M. Pettersson, C. W. Bauschlicher, Jr., and T. Halicioglu, J. Chem. Phys. 87, 2205 (1987).
  15. T. H. Upton, J. Chem. Phys. 86, 7054 (1987).
  16. J. Sun, W. C. Lu, H. Wang, Z.-S. Li, and C.-C. Sun, J. Phys. Chem. A 110, 2729 (2006).
  17. B. K. Rao and P. Jena, J. Chem. Phys. 111, 1890 (1999).
  18. R. Ahlrichs and S. D. Elliott, Phys. Chem. Chem. Phys. 1, 13 (1999).
  19. J. Akola, H. Häkkinen, and M. Manninen, Phys. Rev. B 58, 3601 (1998).
  20. P. Calaminici, N. Russo, and M. Toscano, Z. Phys. D: At., Mol. Clusters 33, 281 (1995).
  21. A. Martínez, A. Vela, and D. R. Salahub, J. Chem. Phys. 101, 10677 (1994).
  22. R. O. Jones, J. Chem. Phys. 99, 1194 (1993).
  23. N. E. Schultz, G. Staszewska, P. Staszewski, and D. G. Truhlar, J. Phys. Chem. B 108, 4850 (2004).
  24. A. W. Jasper, P. Staszewski, G. Staszewska, N. E. Schultz, and D. G. Truhlar, J. Phys. Chem. B 108, 8996 (2004).
  25. G. Staszewska, P. Staszewski, N. E. Schultz, and D. G. Truhlar, Phys. Rev. B 71, 045423 (2005).
  26. N. E. Schultz, and D. G. Truhlar, J. Chem. Theory Comput. 1, 41 (2005).
  27. A. W. Jasper, N. E. Schultz, and D. G. Truhlar, J. Phys. Chem. B 109, 3915 (2005).
  28. D. Bhatt, A. W. Jasper, N. E. Schultz, J. I. Siepmann, and D. G. Truhlar, J. Am. Chem. Soc. 128, 4224 (2006).
  29. D. Bhatt, N. E. Schultz, A. W. Jasper, J. I. Siepmann, and D. G. Truhlar, J. Phys. Chem. B 110, 26135 (2006).
  30. A. W. Jasper, N. E. Schultz, and D. G. Truhlar, J. Chem. Theory Comput. 3, 210 (2007).
  31. H. Li, D. Bhatt, N. E. Schultz, J. I. Siepmann, and D. G. Truhlar, J. Phys. Chem. C 111, 16227 (2007).
  32. H. Li, A. W. Jasper, and D. G. Truhlar, J. Am. Chem. Soc. 129, 14899 (2007).
  33. Z. H. Li and D. G. Truhlar, J. Phys. Chem. C 112, 11109 (2008).
  34. N. E. Schultz, A. W. Jasper, D. Bhatt, J. I. Siepmann, and D. G. Truhlar, in Multiscale Simulation Methods for Nanomaterials, edited by R. B. Ross and S. Mohanty (Wiley-VCH, Hoboken, NJ, 2008), pp. 169–188.
  35. K. Park, D. Lee, A. Rai, D. Mukherjee, and M. R. Zachariah, J. Phys. Chem. B 109, 7290 (2005).
  36. P. W. Villalta and D. G. Leopold, J. Chem. Phys. 130, 024303 (2009).
  37. H. Wu, X. Li, X.-B. Wang, C.-F. Ding, and L.-S. Wang, J. Chem. Phys. 109, 449 (1998).
  38. C.-Y. Cha, G. Ganteför, and W. Eberhardt, J. Chem. Phys. 100, 995 (1994).
  39. Z. Fu, G. W. Lemire, Y. M. Hamrick, S. Taylor, J.-C. Shui, and M. D. Morse, J. Chem. Phys. 88, 3524 (1988).
  40. Z. Fu, L. M. Russon, M. D. Morse, and P. B. Armentrout, Int. J. Mass. Spectrom. 204, 143 (2001).
  41. B. Simard, S. A. Mitchell, D. M. Rayner, and D.-S. Yang, in Metal-Ligand Interactions in Chemistry, Physics and Biology, NATO Science Series, Series C: Mathematical and Physical Sciences Vol. 546, edited by N. Russo and D. R. Salahub (Kluwer, Dordrecht, 2000), pp. 245–248.
  42. S. Li, R. J. Van Zee, and W. Weltner, Jr., Chem. Phys. Lett. 262, 298 (1996).
  43. D. M. Cox, D. J. Trevor, R. L. Whetten, and A. Kaldor, J. Phys. Chem. 92, 421 (1988).
  44. Z. Fu, G. W. Lemire, G. A. Bishea, and M. D. Morse, J. Chem. Phys. 93, 8420 (1990).
  45. GAUSSIAN 03, Revisions C.01 (for NBO 5.G) and D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, et al., Gaussian, Inc., Wallingford CT, 2004 (full citation given in Supporting Information).
  46. M. Ernzerhof and G. E. Scuseria, J. Chem. Phys. 110, 5029 (1999).
  47. C. Adamo and V. Barone, J. Chem. Phys. 110, 6158 (1999).
  48. A. D. McLean and G. S. Chandler, J. Chem. Phys. 72, 5639 (1980).
  49. P. J. Knowles, C. Hampel, and H.-J. Werner, J. Chem. Phys. 99, 5219 (1993).
  50. MOLPRO is a package of ab initio programs written by H.-J. Werner et al., Versions 2002.6 and 2006.1 (full citation given in Supporting Information), see http://www.molpro.net.
  51. H.-J. Werner and P. J. Knowles, MOLPRO User's Manual Version 2006.1, University College, Cardiff Consultants Limited, 2006, Sec. 30.
  52. D. E. Woon and T. H. Dunning, J. Chem. Phys. 98, 1358 (1993).
  53. K. M. Ervin, PESCAL (Versions 2004 and 2008) and FCFGAUS03, FORTRAN programs, http://wolfweb.unr.edu/~ervin/pes/.
  54. K. M. Ervin, T. M. Ramond, G. E. Davico, R. L. Schwartz, S. M. Casey, and W. C. Lineberger, J. Phys. Chem. A 105, 10822 (2001).
  55. K. M. Ervin, J. Ho, and W. C. Lineberger, J. Phys. Chem. 92, 5405 (1988).
  56. K. M. Ervin and W. C. Lineberger, in Advances in Gas Phase Ion Chemistry, edited by N. G. Adams and L. M. Babcock (JAI, Greenwich CT, 1992), Vol. 1, pp. 121–166.
  57. D. W. Kohn, E. S. J. Robles, C. F. Logan, and P. Chen, J. Phys. Chem. 97, 4936 (1993).
  58. P. Chen, in Unimolecular and Bimolecular Reaction Dynamics, edited by C. Y. Ng, T. Baer and I. Powis (Wiley, Chichester, 1994), pp. 402–425.
  59. T. E. Sharp and H. M. Rosenstock, J. Chem. Phys. 41, 3453 (1964).
  60. J. W. Ochterski, http://www.gaussian.com/g_whitepap/vib.htm.
  61. E. Hutchisson, Phys. Rev. 36, 410 (1930).
  62. See EPAPS Document No. E-JCPSA6-129-002842 for the electronic supporting information summarized at the end of this paper. For more information on EPAPS, see http://www.aip.org/pubservs/epaps.html. [EPAPS]
  63. E. B. Wilson, Jr., J. C. Decius, and P. C. Cross, Molecular Vibrations (Dover, New York, 1980; McGraw-Hill, 1955).
  64. T. C. Thompson, D. G. Truhlar, and C. A. Mead, J. Chem. Phys. 82, 2392 (1985).
  65. E. Miyoshi, H. Tatewaki, and T. Nakamura, J. Chem. Phys. 78, 815 (1983).
  66. I. Sioutis, V. L. Stakhursky, R. M. Pitzer, and T. A. Miller, J. Chem. Phys. 126, 124308 (2007).
  67. N. Lambert, N. Kaltsoyannis, S. D. Price, J. Žabka, and Z. Herman, J. Phys. Chem. A 110, 2898 (2006).
  68. J. C. Rienstra-Kiracofe, W. D. Allen, and H. F. Schaefer III, J. Phys. Chem. A 104, 9823 (2000).
  69. C. C. Cramer, Essentials of Computational Chemistry, 2nd Ed. (Wiley, Chichester, 2004).
  70. E. D. Glendening, J. K. Badenhoop, A. E. Reed, J. E. Carpenter, J. A. Bohmann, C. M. Morales, and F. Weinhold, NBO 5.G, Theoretical Chemistry Institute, University of Wisconsin, Madison, WI, 2001, http://www.chem.wisc.edu/~nbo5.
  71. F. Weinhold and C. Landis, Valency and Bonding: A Natural Bond Orbital Donor-Acceptor Perspective (Cambridge University Press, Cambridge, 2005).
  72. G. L. Gutsev and C. W. Bauschlicher, Jr., J. Phys. Chem. A 107, 4755 (2003).
  73. X. Li, H. Wu, X.-B. Wang, and L.-S. Wang, Phys. Rev. Lett. 81, 1909 (1998).
  74. J. C. Rienstra-Kiracofe, G. S. Tschumper, and H. F. Schaefer III, Chem. Rev. (Washington, D.C.) 102, 231 (2002).
  75. T. Andersen, H. K. Haugen, and H. Hotop, J. Phys. Chem. Ref. Data 28, 1511 (1999).
  76. V. Kaufman and W. C. Martin, J. Phys. Chem. Ref. Data 20, 775 (1991), http://physics.nist.gov/PhysRefData/Handbook/Tables/aluminumtable1.htm.
  77. J. E. Harrington and J. C. Weisshaar, J. Chem. Phys. 93, 854 (1990).
  78. F. Chau, J. M. Dyke, E. P. Lee, and D. Wang, J. Electron Spectrosc. Relat. Phenom. 97, 33 (1998).
  79. D. K. W. Mok, E. P. F. Lee, F. Chau, D. Wang, and J. M. Dyke, J. Chem. Phys. 113, 5791 (2000).
  80. F. Chau, D. K. W. Mok, E. P. F. Lee, and J. M. Dyke, ChemPhysChem 6, 2037 (2005).
  81. J. M. Dyke, E. P. F. Lee, D. K. W. Mok, and F. Chau, ChemPhysChem 6, 2046 (2005).
  82. J. S. Guss, C. A. Richmond, K. Nauta, and S. H. Kable, Phys. Chem. Chem. Phys. 7, 100 (2005).
  83. T. Leyssens, D. Peeters, A. G. Orpen, and J. N. Harvey, New J. Phys. 29, 1424 (2005).
  84. P. Geerlings, F. De Proft, and W. Langenaeker, Chem. Rev. (Washington, D.C.) 103, 1793 (2003).

CITING ARTICLES
For access to citing articles, you need to log in.
For access to citing articles, you need to Log in.


Copyright © American Institute of Physics