Theoretical study of ladder polysilanes

Organometallics

Volumn 26, Issue 11, 2007, Pages 2806-2814

  Kosa, Monica ^a   Karni, Miriam ^a   Apeloig, Yitzhak ^a  

^a TECHNION ISRAEL INSTITUTE OF TECHNOLOGY   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

DENSITY FUNCTIONAL THEORY; DERIVATIVES; ELECTRONIC PROPERTIES; QUANTUM THEORY; WAVELENGTH;

CATENATION; CYCLOTETRASILANE RINGS; ENERGY TRANSITIONS; OLIGOSILANES;

POLYSILANES;

EID: 34249951501     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om0610344     Document Type: Article

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45. - (n = 1) was calculated also using a larger basis set, including diffuse functions, at the UB3LYP/6-31G+(d) level. At this level of theory, the three bridging Si-Si bond lengths are 2.381, 2.363, and 2.381 A, while the longitudinal Si-Si bonds are 2.385 and 2.376 Å. Increasing the basis set from 6-31G(d) to 6-31G+(d) shortens the bridging Si-Si bonds while lengthening the longitudinal Si-Si bonds.
46. 2 = 0.999). For details see Figure 2S in the Supporting Information.
47. This work will be published elsewhere.
48. (a) Transition states were not located.
49. (b) The reliability of the UB3LYP energies for calculating singlet 1,4-biradicals was tested for the model biradical 1 (R = H, n = 1) by comparison with several high-level ab initio and DFT methods. Similar trends in the relative energies of bicyclic 1 (n = 1) and of biradical 1′ (R = H, n = 1) were calculated by DFT or ab initio methods. For example, the biradical 1′ (R = H, n = 1) lies 47.6, 45.8, and 31.9 kcal/mol above the bicyclic 1 (R = H, n = 1) at UB3LYP/ 6-31G(d)//UB3LYP/6-31G(d), UMP2/6-31G(d)//UMP2/6-31G(d) and CAS-(6,6)/6-31G(d)// CAS(6,6)/6-31G(d) levels of theory, respectively. We have also found that the UB3LYP/6-31G(d) and UB3LYP/6-311+G(3d) geometries and relative energies of all the species on the PES for the isomerization of syn-1 (R = H, n = 2) to anti-1 (R = H, n = 2) (closed shell and biradicals) are very similar, justifying the use of the smaller basis set for 2 (R = Me, n = 2).
50. 2〉 expectation value is 0.9 for both syn-2′ and anti-2′. Since the energies of triplet syn-2′ and anti-2′ are very close to those of the pure singlet state energies, the energies calculated for pure and contaminated wave functions are nearly the same (energy difference of ca. ±0.2 kcal/mol). For a formula of how to calculate the energy of a pure singlet state and a discussion see: Gräfenstein, J.; Hjerpe, A. M.; Kraka, E.; Cremer, D. J. Phys. Chem. A 2000, 104, 1748.
51. (a) For calculated Si-Si bond energies see: Karni, M.; Apeloig, Y.; Kapp, J.; Schleyer, P. v. R. In The Chemistry of Organic Silicon Compounds; Rappoport, Z., Apeloig, Y., Eds.; Wiley: Chichester, U.K., 2001; Vol. 3, Chapter 1, p 1.
52. (b) For experimental Si-Si bond energies see: Walsh, R. In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; Wiley: Chichester, U.K., 1989; Chapter 5, p 371.