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CHARACTERIZATION of the SiC 3 H - anion N. Inostroza 1, M. L. Senent 1 1 Instituto de Estructura de la Materia, C.S.I.C, Departamento de Astrofísica Molecular.

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Presentation on theme: "CHARACTERIZATION of the SiC 3 H - anion N. Inostroza 1, M. L. Senent 1 1 Instituto de Estructura de la Materia, C.S.I.C, Departamento de Astrofísica Molecular."— Presentation transcript:

1 CHARACTERIZATION of the SiC 3 H - anion N. Inostroza 1, M. L. Senent 1 1 Instituto de Estructura de la Materia, C.S.I.C, Departamento de Astrofísica Molecular e Infrarroja,, Serrano 121 Madrid 28006,España. 2 Columbus, Ohio 21-25 June, 2010 The 65 th International Symposium on Molecular Spectroscopy

2 Silicon Carbon Chains: Relevance Chemistry 1)Material Chemistry: Silicon carbon molecules are components of many semiconductor devices. Laboratory detection of small silicon carbon molecules (McCarthy et.al 2003) 2) Molecular Astrophysics: Silicon carbon molecules have been identified in gas phase. (Si is a major constituent of interstellar dust but exist in gas phase)

3 SiC 3 / C 4 SiC 3 H - isovalent to C 4 H - N.Inostroza, et.al. A&A (2008), C4H- has been one of the first anions detected. Cernicharo, J. et.al, ApJ. 2002 Neutral C 4 H was detected 20 years early. The hydrogen-bearing silicon carbide radicals SiC n H are isovalent to C n+1 H species. SiC 3 H -

4 neutral  anion  EaEa CSi (X 3  ) 0.8831l-CSi - (X 2  + ) 11.59212.42 c-C 2 Si(X 1 A 1 )2.9587l-C 2 Si - (X 2  ) 5.69311.41 c-C 3 Si(X 1 A 1 )3.8671 l-C 3 Si - (X 2  ) 2.4308 2.49 2.89 l-C 3 Si (X 3  - ) 4.4016 l-C 4 Si (X 1  + ) 6.2111l-C 4 Si - (X 2  ) 2.23492.31 l-C 5 Si (X 3  - ) 6.4927l-C 5 Si - (X 2  ) 5.27653.30 l-SiCH (X 2  ) 0.5771l-SiCH - (X 1  + ) 12.38753.88 l-SiC 2 H (X 2  ) 1.1201l-SiC 2 H - (X 3  - ) 1.36511.32 l-SiC 3 H (X 2  ) 1.1074l-SiC 3 H - (X 1  + ) 9.30232.70 l-SiC 4 H (X 2  ) 1.3061l-SiC 4 H - (X 3  - ) 10.89131.69 l-SiC 5 H(X 2  )0.5122l-SiC 5 H - (X 1  + )4.89912.98

5 neutral  anion  EaEa CSi (X 3  ) 0.8831l-CSi - (X 2  + ) 11.59212.42 c-C 2 Si(X 1 A 1 )2.9587l-C 2 Si - (X 2  ) 5.69311.41 c-C 3 Si(X 1 A 1 )3.8671 l-C 3 Si - (X 2  ) 2.4308 2.49 2.89 l-C 3 Si (X 3  - ) 4.4016 l-C 4 Si (X 1  + ) 6.2111l-C 4 Si - (X 2  ) 2.23492.31 l-C 5 Si (X 3  - ) 6.4927l-C 5 Si - (X 2  ) 5.27653.30 l-SiCH (X 2  ) 0.5771l-SiCH - (X 1  + ) 12.38753.88 l-SiC 2 H (X 2  ) 1.1201l-SiC 2 H - (X 3  - ) 1.36511.32 l-SiC 3 H (X 2  ) 1.1074l-SiC 3 H - (X 1  + ) 9.30232.70 l-SiC 4 H (X 2  ) 1.3061l-SiC 4 H - (X 3  - ) 10.89131.69 l-SiC 5 H(X 2  )0.5122l-SiC 5 H - (X 1  + )4.89912.98

6 neutral  anion  EaEa CSi (X 3  ) 0.8831l-CSi - (X 2  + ) 11.59212.42 c-C 2 Si(X 1 A 1 )2.9587l-C 2 Si - (X 2  ) 5.69311.41 c-C 3 Si(X 1 A 1 )3.8671 l-C 3 Si - (X 2  ) 2.4308 2.49 2.89 l-C 3 Si (X 3  - ) 4.4016 l-C 4 Si (X 1  + ) 6.2111l-C 4 Si - (X 2  ) 2.23492.31 l-C 5 Si (X 3  - ) 6.4927l-C 5 Si - (X 2  ) 5.27653.30 l-SiCH (X 2  ) 0.5771l-SiCH - (X 1  + ) 12.38753.88 l-SiC 2 H (X 2  ) 1.1201l-SiC 2 H - (X 3  - ) 1.36511.32 l-SiC 3 H (X 2  ) 1.1074l-SiC 3 H - (X 1  + ) 9.30232.70 l-SiC 4 H (X 2  ) 1.3061l-SiC 4 H - (X 3  - ) 10.89131.69 l-SiC 5 H(X 2  )0.5122l-SiC 5 H - (X 1  + )4.89912.98

7 neutral  anion  EaEa CSi (X 3  ) 0.8831l-CSi - (X 2  + ) 11.59212.42 c-C 2 Si(X 1 A 1 )2.9587l-C 2 Si - (X 2  ) 5.69311.41 c-C 3 Si(X 1 A 1 )3.8671 l-C 3 Si - (X 2  ) 2.4308 2.49 2.89 l-C 3 Si (X 3  - ) 4.4016 l-C 4 Si (X 1  + ) 6.2111l-C 4 Si - (X 2  ) 2.23492.31 l-C 5 Si (X 3  - ) 6.4927l-C 5 Si - (X 2  ) 5.27653.30 l-SiCH (X 2  ) 0.5771l-SiCH - (X 1  + ) 12.38753.88 l-SiC 2 H (X 2  ) 1.1201l-SiC 2 H - (X 3  - ) 1.36511.32 l-SiC 3 H (X 2  ) 1.1074l-SiC 3 H - (X 1  + ) 9.30232.70 l-SiC 4 H (X 2  ) 1.3061l-SiC 4 H - (X 3  - ) 10.89131.69 l-SiC 5 H(X 2  )0.5122l-SiC 5 H - (X 1  + )4.89912.98

8 neutral  anion  EaEa CSi (X 3  ) 0.8831l-CSi - (X 2  + ) 11.59212.42 c-C 2 Si(X 1 A 1 )2.9587l-C 2 Si - (X 2  ) 5.69311.41 c-C 3 Si(X 1 A 1 )3.8671 l-C 3 Si - (X 2  ) 2.4308 2.49 2.89 l-C 3 Si (X 3  - ) 4.4016 l-C 4 Si (X 1  + ) 6.2111l-C 4 Si - (X 2  ) 2.23492.31 l-C 5 Si (X 3  - ) 6.4927l-C 5 Si - (X 2  ) 5.27653.30 l-SiCH (X 2  ) 0.5771l-SiCH - (X 1  + ) 12.38753.88 l-SiC 2 H (X 2  ) 1.1201l-SiC 2 H - (X 3  - ) 1.36511.32 l-SiC 3 H (X 2  ) 1.1074l-SiC 3 H - (X 1  + ) 9.30232.70 l-SiC 4 H (X 2  ) 1.3061l-SiC 4 H - (X 3  - ) 10.89131.69 l-SiC 5 H(X 2  )0.5122l-SiC 5 H - (X 1  + )4.89912.98

9 neutral  anion  EaEa CSi (X 3  ) 0.8831l-CSi - (X 2  + ) 11.59212.42 c-C 2 Si(X 1 A 1 )2.9587l-C 2 Si - (X 2  ) 5.69311.41 c-C 3 Si(X 1 A 1 )3.8671 l-C 3 Si - (X 2  ) 2.4308 2.49 2.89 l-C 3 Si (X 3  - ) 4.4016 l-C 4 Si (X 1  + ) 6.2111l-C 4 Si - (X 2  ) 2.23492.31 l-C 5 Si (X 3  - ) 6.4927l-C 5 Si - (X 2  ) 5.27653.30 l-SiCH (X 2  ) 0.5771l-SiCH - (X 1  + ) 12.38753.88 l-SiC 2 H (X 2  ) 1.1201l-SiC 2 H - (X 3  - ) 1.36511.32 l-SiC 3 H (X 2  ) 1.1074l-SiC 3 H - (X 1  + ) 9.30232.70 l-SiC 4 H (X 2  ) 1.3061l-SiC 4 H - (X 3  - ) 10.89131.69 l-SiC 5 H(X 2  )0.5122l-SiC 5 H - (X 1  + )4.89912.98 Ea  RCCSD(T)-F12A/aug-cc-pVTZ

10 neutral  anion  EaEa CSi (X 3  ) 0.8831l-CSi - (X 2  + ) 11.59212.42 c-C 2 Si(X 1 A 1 )2.9587l-C 2 Si - (X 2  ) 5.69311.41 c-C 3 Si(X 1 A 1 )3.8671 l-C 3 Si - (X 2  ) 2.4308 2.49 2.89 l-C 3 Si (X 3  - ) 4.4016 l-C 4 Si (X 1  + ) 6.2111l-C 4 Si - (X 2  ) 2.23492.31 l-C 5 Si (X 3  - ) 6.4927l-C 5 Si - (X 2  ) 5.27653.30 l-SiCH (X 2  ) 0.5771l-SiCH - (X 1  + ) 12.38753.88 l-SiC 2 H (X 2  ) 1.1201l-SiC 2 H - (X 3  - ) 1.36511.32 l-SiC 3 H (X 2  ) 1.1074l-SiC 3 H - (X 1  + ) 9.30232.70 l-SiC 4 H (X 2  ) 1.3061l-SiC 4 H - (X 3  - ) 10.89131.69 l-SiC 5 H(X 2  )0.5122l-SiC 5 H - (X 1  + )4.89912.98

11 neutral  anion  EaEa CSi (X 3  ) 0.8831l-CSi - (X 2  + ) 11.59212.42 c-C 2 Si(X 1 A 1 )2.9587l-C 2 Si - (X 2  ) 5.69311.41 c-C 3 Si(X 1 A 1 )3.8671 l-C 3 Si - (X 2  ) 2.4308 2.49 2.89 l-C 3 Si (X 3  - ) 4.4016 l-C 4 Si (X 1  + ) 6.2111l-C 4 Si - (X 2  ) 2.23492.31 l-C 5 Si (X 3  - ) 6.4927l-C 5 Si - (X 2  ) 5.27653.30 l-SiCH (X 2  ) 0.5771l-SiCH - (X 1  + ) 12.38753.88 l-SiC 2 H (X 2  ) 1.1201l-SiC 2 H - (X 3  - ) 1.36511.32 l-SiC 3 H (X 2  ) 1.1074l-SiC 3 H - (X 1  + ) 9.30232.70 l-SiC 4 H (X 2  ) 1.3061l-SiC 4 H - (X 3  - ) 10.89131.69 l-SiC 5 H(X 2  )0.5122l-SiC 5 H - (X 1  + )4.89912.98   CASSCF/aug-cc-pVTZ

12 neutral  anion  EaEa CSi (X 3  ) 0.8831l-CSi - (X 2  + ) 11.59212.42 c-C 2 Si(X 1 A 1 )2.9587l-C 2 Si - (X 2  ) 5.69311.41 c-C 3 Si(X 1 A 1 )3.8671 l-C 3 Si - (X 2  ) 2.4308 2.49 2.89 l-C 3 Si (X 3  - ) 4.4016 l-C 4 Si (X 1  + ) 6.2111l-C 4 Si - (X 2  ) 2.23492.31 l-C 5 Si (X 3  - ) 6.4927l-C 5 Si - (X 2  ) 5.27653.30 l-SiCH (X 2  ) 0.5771l-SiCH - (X 1  + ) 12.38753.88 l-SiC 2 H (X 2  ) 1.1201l-SiC 2 H - (X 3  - ) 1.36511.32 l-SiC 3 H (X 2  ) 1.1074l-SiC 3 H - (X 1  + ) 9.30232.70 l-SiC 4 H (X 2  ) 1.3061l-SiC 4 H - (X 3  - ) 10.89131.69 l-SiC 5 H(X 2  )0.5122l-SiC 5 H - (X 1  + )4.89912.98   CASSCF/aug-cc-pVTZ

13 neutral  anion  EaEa CSi (X 3  ) 0.8831l-CSi - (X 2  + ) 11.59212.42 c-C 2 Si(X 1 A 1 )2.9587l-C 2 Si - (X 2  ) 5.69311.41 c-C 3 Si(X 1 A 1 )3.8671 l-C 3 Si - (X 2  ) 2.4308 2.49 2.89 l-C 3 Si (X 3  - ) 4.4016 l-C 4 Si (X 1  + ) 6.2111l-C 4 Si - (X 2  ) 2.23492.31 l-C 5 Si (X 3  - ) 6.4927l-C 5 Si - (X 2  ) 5.27653.30 l-SiCH (X 2  ) 0.5771l-SiCH - (X 1  + ) 12.38753.88 l-SiC 2 H (X 2  ) 1.1201l-SiC 2 H - (X 3  - ) 1.36511.32 l-SiC 3 H (X 2  ) 1.1074l-SiC 3 H - (X 1  + ) 9.30232.70 l-SiC 4 H (X 2  ) 1.3061l-SiC 4 H - (X 3  - ) 10.89131.69 l-SiC 5 H(X 2  )0.5122l-SiC 5 H - (X 1  + )4.89912.98 C4H-C4H- C2H-C2H- C6H-C6H-

14 neutral  anion  EaEa CSi (X 3  ) 0.8831l-CSi - (X 2  + ) 11.59212.42 c-C 2 Si(X 1 A 1 )2.9587l-C 2 Si - (X 2  ) 5.69311.41 c-C 3 Si(X 1 A 1 )3.8671 l-C 3 Si - (X 2  ) 2.4308 2.49 2.89 l-C 3 Si (X 3  - ) 4.4016 l-C 4 Si (X 1  + ) 6.2111l-C 4 Si - (X 2  ) 2.23492.31 l-C 5 Si (X 3  - ) 6.4927l-C 5 Si - (X 2  ) 5.27653.30 l-SiCH (X 2  ) 0.5771l-SiCH - (X 1  + ) 12.38753.88 l-SiC 2 H (X 2  ) 1.1201l-SiC 2 H - (X 3  - ) 1.36511.32 l-SiC 3 H (X 2  ) 1.1074l-SiC 3 H - (X 1  + ) 9.30232.70 l-SiC 4 H (X 2  ) 1.3061l-SiC 4 H - (X 3  - ) 10.89131.69 l-SiC 5 H(X 2  )0.5122l-SiC 5 H - (X 1  + )4.89912.98 C4H-C4H-

15 Isomers of SiC 3 H - l-SiC 3 H - X 1  + c-SiC 3 H - X 1 A’ l1-SiC 3 H - X 1 A’ c1-SiC 3 H - X 1 A’ c3-SiC 3 H - X 1 A’ l2-SiC 3 H - X 1 A’ c4-SiC 3 H - X 1 A c5-SiC 3 H - X 1 A’ c6-SiC 3 H - X 1 A’ c7-SiC 3 H - X 1 A’ l3-SiC 3 H - X 1 A’ c2-SiC 3 H - X 1 A’

16 Isomers of SiC 3 H - l-SiC 3 H - X 1  + c-SiC 3 H - X 1 A’ l1-SiC 3 H - X 1 A’ c1-SiC 3 H - X 1 A’ c3-SiC 3 H - X 1 A’ l2-SiC 3 H - X 1 A’ c4-SiC 3 H - X 1 A c5-SiC 3 H - X 1 A’ c6-SiC 3 H - X 1 A’ c7-SiC 3 H - X 1 A’ l3-SiC 3 H - X 1 A’ c2-SiC 3 H - X 1 A’

17 Isomers of SiC 3 H - l-SiC 3 H - X 1  + Er=0.0 c-SiC 3 H - X 1 A’ Er=1.15 l1-SiC 3 H - X 1 A’ Er=1.70 c1-SiC 3 H - X 1 A’ Er=1.86 c3-SiC 3 H - X 1 A’ Er=1.92 l2-SiC 3 H - X 1 A’ Er=2.04 c4-SiC 3 H - X 1 A Er=2.06 c5-SiC 3 H - X 1 A’ Er=2.14 c6-SiC 3 H - X 1 A’ Er=2.43 c7-SiC 3 H - X 1 A’ Er=2.63 l3-SiC 3 H - X 1 A’ Er=2.80 c2-SiC 3 H - X 1 A’ Er=1.92 RCCSD(T)/CASSCF aug-cc-pVTZ

18 Isomers of SiC 3 H - l-SiC 3 H - X 1  + Er=0.0 c-SiC 3 H - X 1 A’ Er=1.15 l1-SiC 3 H - X 1 A’ Er=1.70 c1-SiC 3 H - X 1 A’ Er=1.86 RCCSD(T)/CASSCF aug-cc-pVTZ c3-SiC 3 H - X 1 A’ Er=1.92 l2-SiC 3 H - X 1 A’ Er=2.04 c4-SiC 3 H - X 1 A Er=2.06 c5-SiC 3 H - X 1 A’ Er=2.14 c6-SiC 3 H - X 1 A’ Er=2.43 c7-SiC 3 H - X 1 A’ Er=2.63 l3-SiC 3 H - X 1 A’ Er=2.80 c2-SiC 3 H - X 1 A’ Er=1.92

19 Basis setnana l-SiC 3 H - B e l-SiC 3 D - B e RCCSD(T)-F12A aug-cc-pVTZ 82598.332438.24 aug-cc-pVTZ82578.132419.55 aug-cc-pVQZ82594.032434.29 aug-cc-pV5Z82599.572439.36 CBS b 2605.162444.36 aug-cc-pCVQZ42603.002442.46 aug-cc-pCVQZ12611.512450.45 a) n=number of frozen core orbitals b) CBS =complete basis set ( aug-cc-pV  Z)  = 13.59 Debyes CASSCF/aug-cc-pV5Z  B e core  17 MHz  B vib  2 MHz B 0 (l-SiC 3 H - )=2620.74 MHz  B e core = B e (aug-cc-pCVQZ, n=1) - B e (aug-cc-pVQZ, n=8) B 0 = B e CBS +  B e core +  B vib B e =B e CBS + B e 1 (X+1) -3 + B e 2 (X+1) -5 + …… B 0 (l-SiC 3 D - )= 2459.81 MHz Dipole moment and rotational constant

20 Vertical excitation energies of l-SiC 3 H - Sym Er MRCI Sym E MRCI X2X2 0.0 b 1+1+ 0.0 d 2+2+ 2.01 11 3.09 22 5.66 11 3.29 2-2- 5.43 1-1- 3.22 4+4+ 3.43 3+3+ 2.48 44 3.82 33 3.10 4-4- 4.19 33 2.66 44 2.21 3-3- 2.85 MRCI/aug-cc-pVTZ c) Ea=-493.205588 a.u.; d) Ea=-403.597248 a.u. Ea= 2.70 eV

21 Vertical excitation energies of l-SiC 3 H - Sym Er MRCI Sym E MRCI X2X2 0.0 b 1+1+ 0.0 d 2+2+ 2.01 11 3.09 22 5.66 11 3.29 2-2- 5.43 1-1- 3.22 4+4+ 3.43 3+3+ 2.48 44 3.82 33 3.10 4-4- 4.19 33 2.66 44 2.21 3-3- 2.85 MRCI/aug-cc-pVTZ c) Ea=-493.205588 a.u.; d) Ea=-403.597248 a.u. Ea= 2.70 eV

22 Vertical excitation energies of l-SiC 3 H - Sym Er MRCI Sym E MRCI X2X2 0.0 b 1+1+ 0.0 d 2+2+ 2.01 11 3.09 22 5.66 11 3.29 2-2- 5.43 1-1- 3.22 4+4+ 3.43 3+3+ 2.48 44 3.82 33 3.10 4-4- 4.19 33 2.66 44 2.21 3-3- 2.85 MRCI/aug-cc-pVTZ c) Ea=-493.205588 a.u.; d) Ea=-403.597248 a.u. Ea= 2.70 eV

23 Potential Energy Surface PES Definition of linear angles (Hoy et. al Mol.Phys.1972) RCCSD(T)-F12/ cc-pVTZ-F12 GRID 1409 geometries : Bond distances R ref +0.03 Å ≥ R ≥ R ref -0.03 Å Torsional angles  re f + 5.0 o ≥  ≥  re f – 5.0° Planar bending angles=  +5.0º FIT R 2 =1.0,  =0.4 cm -1

24 Spectroscopic Parameters

25 Spectroscopic Parameters

26 Spectroscopic Parameters

27 Spectroscopic Parameters

28 Spectroscopic Parameters

29 Spectroscopic Parameters

30 Spectroscopic Parameters

31 Spectroscopic Parameters

32 Conclusions  The formation of SiC3H - seems to be viable on the basis of our calculations  = 13.59 Debyes  B 0 =2620.74 MHz  = 13.59 Debyes  We hope that the future astronomical observatory ALMA will find our molecule  SiC 3 H is strongly stabilized by electron attachment

33 ACKNOWLEGMENTS The authors acknowledge the Ministerio de Ciencia e Innovaci ó n of SPAIN for grants (AYA2008-00446 and AYA2009-05801-E/AYA) and also to CESGA for computing facilities. Thank you for your attention !

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