Rydberg, valence, and ion pair quintet states of O 2

Transcription

1 Rydberg, valence, and ion pair quintet states of O 2 Gabriel J. Vázquez 1 H. P. Liebermann 2 H. Lefebvre Brion 3 1 Universidad Nacional Autónoma de México Cuernavaca, México 2 Bergische Universität Wuppertal, Germany 3 Université de Paris Sud Orsay, France 70 th ISMS University of Illinois, June 201 () 1 / 1

2 Outline Details of calculations Sample of O 2, O + 2 and O++ 2 PECs and spectroscopic constants Overview of the valence, ion pair, and Rydberg quintet states Spectroscopic constants of valence states Spectroscopic constants of ion pair states Tentative attribution of Rydberg states of series converging to the a 4 Π u, b 4 Σ g, f4 Π g and 6 Σ + u states of O+ 2 Conclusions () 2 / 1

3 Ab initio electronic structure calculations of O 2 and O + 2 Type: SCF MRSD(TQ) CI SCF: D 2h symmetry Package: MRD CI a Core: 1σ 2 g 1σ2 u 1s(O 1 ) and 1s(O 2 ) O basis: cc pvqz + CI: 12 active e diffuse (three s, three p, one d) Functions: O(8s7p4d2f) Excitations: S + D + (T, Q) Total O 2 16s14p8d4f MO s O 2 (X 3 Σ g ) 146 atomic functions Conf. O 2 (X) 1σ 2 g 1σ2 u 2σ2 g 2σ2 u 3σ2 g 1π4 u 1π2 g a Bonn-Wuppertal package, Buenker & Peyerimhoff () 1 / 1

4 ev Σ + g O + ( 4 S)+O + ( 4 S) O O + ( 4 S)+O ( 3 P) O Πg 10 3 Σ g O ( 3 P)+O ( 3 P) R (Ang.) () 16 / 1 O 2

5 Spectroscopic constants of selected states of O 2, O + and O a. System State AIE r e ω e B e D e ev Å cm 1 cm 1 ev O ++ 2 X 1 Σ + g (1.07) (2089) (1.82) O + 2 A 2 Π u (1.419) 898 (913) 1.061(1.046) 1.76 (1.4) a 4 Π u (1.389) 1036 (1060) 1.104(1.092) 2.69 (2.4) X 2 Π g (1.132) 190 (189) 1.691(1.64) 6.78 (6.36) O 2 X 3 Σ g (1.216) (164) 1.437(1.424).21 (.09) a Theoretical values in parenthesis. () 17 / 1

6 Molecular states correlating to the lowest dissociation limits of O 2, along with their respective dissociation energies. a Molecular states Limit Limit D 0 (ev) a number 2,4,6 [Σ +, Π]g,u O + ( 4 S)+O( 3 P) , [Σ +, Π]g,u O + ( 4 S ) +O ( 2 P) ,,7 [Σ +, Π]g,u O( 3 P)+O( S ) [Σ, Π, ]g,u O( 1 D)+O( 3 S ) [Σ, Π, ]g,u O( 1 D)+O( S ) , [Σ + (2), ]g, 3 [Σ + (2), ] u, 1, [Σ ] u, 3 [Σ ] g, 1,3, [Π] g,u O( 3 P)+O( 3 P) [Σ + (2), Σ, Π(2), ]g,u O( 3 P)+O( P) ,3, [Σ +, Π]g,u O( 3 P)+O( 3 S ) ,3,,7 [Σ +, Π]g,u O( 3 P)+O( S ) [Σ + ]g O( 1 S)+O( 1 S) [Σ +, Π, ]g,u O( 1 D)+O( 1 S) [Σ, Π]g,u O( 3 P)+O( 1 S) [Σ + (3), (2), Γ]g, 1 [Σ (2), ] u, 1 [Π(2), Φ] g,u O( 1 D)+O( 1 D) [Σ +, Σ (2), Π(3), (2), Φ]g,u O( 3 P)+O( 1 D) , [Σ + (2), ]g, 3 [Σ + (2), ] u, 1, [Σ ] u, 3 [Σ ] g, 1,3, [Π] g,u O( 3 P)+O( 3 P) 1.11 a Energies are referred with respect to O 2(X 3 Σ g, v = 0). () 20 / 1

7 E(eV) 12 Ag Au B1g B1u B2g B3u R (a.u.) () 30 / 1

8 E(eV) Ag Au B1g B1u B2g B3u R (a.u.) () 31 / 1

9 E(eV) Ag Au B1g B1u B2g B3u Σ u Πg Σ + g Σ + g Πu g 3 3 O ( P) + O ( P) 2 X 3 Σ g R (a.u.) () 32 / 1

10 E(eV) Ag Au B1g B1u B2g B3u R (a.u.) () 33 / 1

11 () 34 / 1

12 E(eV) Σ + g 1 10 X 3 Σ g R (a.u.) () 3 / 1

13 E(eV) Σ u 1 u 10 X 3 Σ g R (a.u.) () 36 / 1

14 E(eV) Σ g g (2) 1 10 g X 3 Σ g R (a.u.) () 37 / 1

15 E(eV) Σ + u 1 10 X 3 Σ g R (a.u.) () 38 / 1

16 E(eV) Πg 1 10 X 3 Σ g R (a.u.) () 39 / 1

17 E(eV) Πu 1 10 X 3 Σ g R (a.u.) () 40 / 1

18 Table: Spectroscopic constants of the six valence quintet states of O 2 dissociating into ground state atoms State T e R e D e Authors (ev) (a.u) (cm 1 ) Σ + g This work or b unstable Liu et. al Σ + g This work unstable Saxon & Liu Σ u This work 6.19 or Partridge et al van Vroonhoven et al Liu et. al Πu This work Partridge et al van Vroonhoven et al. Πg This work 4.2 or Partridge et al Liu et. al g This work () 0 / 1

19 Table: Spectroscopic constants of the ion pair states of O 2 dissociating into O + ( 4 S)+O ( 2 P) at ev State T e R e ω e ω e x e Authors (ev) (a.u.) (cm 1 ) (cm 1 ) Σ g This work krauss & neumann Σ u This work krauss & neumann zhou et al. Πu This work zhou et al. Πg This work () 1 / 1

20 Table: Tentative attribution of quintet Rydberg states with the a 4 Π u core a (IP=16.16 ev) State T e R e n a Dominant (ev) (a.u.) configuration Πu (a 4 Π u) 3sσ g Σ + g (a 4 Π u) 3pπ u Πg (a 4 Π u) 3pσ u Πu (a 4 Π u) 3dσ g Σu (a 4 Π u) 3dπ g u (a 4 Π u) 3dπ g Πu (a 4 Π u) 3dδ g Πu (a 4 Π u) 3dσ g g (a 4 Π u) 4pπ u Πg (a 4 Π u) 4pσ u Πu (a 4 Π u) 4sσ g Πu (a 4 Π u) 4dσ g Σ u (a 4 Π u) 4dπ g u ( a 4 Π u) 4dπ g Πu ( a 4 Π u) 4dδ g () 2 / 1

21 Table: Tentative attribution of quintet Rydberg states with the b 4 Σ g corea (IP= ev) State T e R e n a Dominant (ev) (a.u.) configuration Σ g (b 4 Σ g ) 3sσg Σ u (b 4 Σ g ) 3pσu Πu (b 4 Σ g ) 3pπu Σ g ( b 4 Σ g ) 3dσg Πg (b 4 Σ g ) 3dπg Σ g ( b 4 Σ g ) 4sσg Σ u (b 4 Σ g ) 4pσu () 3 / 1

22 Table: Quintet Rydberg states with the f 4 Π g core (IP= ev) State T e R e n a Dominant (ev) (a.u.) configuration Πg (f 4 Π g ) 3sσ g Πu (f 4 Π g ) 3pσ u Σ + u (f 4 Π g ) 3pπ u u (f 4 Π g ) 3dπ g () 4 / 1

23 Table: Quintet Rydberg states with the 6 Σ + u corea (IP= 17.1 ev) State T e R e n a Dominant (ev) (a.u.) configuration Σ + u ( 6 Σ + u ) 3sσg Σ + u ( 6 Σ + u ) 3dσg Σ + u ( 6 Σ + u ) 4sσg () / 1

24 () 6 / 1

25 B2g 17.0 E / ev R (a.u.) () 67 / 1

26 B3u 16. E / ev R (a.u.) () 68 / 1

27 E(eV) LI&LEWE[IPP SJbI: 16 &Y R (a.u.) () 69 / 1

28 E(eV) &Y 8LI&YLEWE[IPP SJbI: -XMWWSQI[LEXYRI\TIGXIH WMRGIXLILMKLQYPXMTPMGMX] WXEXIWEVIQSWXSJXIR YRFSYRH R (a.u.) () 70 / 1

29 Summary A comprehensive ab initio study of many electronic states of O 2, O + and O++ is currently underway 2 2 PECs of about 10 electronic states of O 2, 100 of O +, and 20 of O Valence, Rydberg, ion pair states Spectroscopic constants (T e, T v, ω e, ω ex e, B e, D e, D 0, µ functions, IP s, etc.) The calculation revealed a rich electronic structure of high spin states (s, 6s, 7s) Information on O 2 quintet states Numerous bound Rydberg states are reported Rydberg orbitals have been attributed tentatively to various quintet states Spectroscopic constants of the six repulsive (or weakly bound) valence quintet states ( Σ + g (2), Σ u, Π u, Π g, A g) Spectroscopic constants of the four ( Σ + g, Σ u, Π g, Π u) ion pair states () 77 / 1

30 Acknowledgements Work supported by Universidad Nacional Autónoma de México (UNAM) through DGAPA PASPA GJV would like to thank Prof. Yuxiang Mo of the Department of Physics of Tsinghua University, and to Dr. J. J. Wang, of the National Astronomical Observatories of China, Beijing, for hosting him during his sabbatical year J.M. Amero for help with the preparation of this presentation () 79 / 1

31 T H A N K S () 80 / 1