Theoretical Chemistry Accounts

, Volume 128, Issue 4–6, pp 783–793 | Cite as

Theoretical study of the role of solvent Stark effect in electron transitions

  • M. Elena Martín
  • M. Luz Sánchez
  • José C. Corchado
  • Aurora Muñoz-Losa
  • Ignacio Fdez. Galván
  • Francisco J. Olivares del Valle
  • Manuel A. Aguilar
Regular Article

Abstract

The possible influence of the solvent Stark effect (SSE) on the solvatochromic shift in electron transitions has been analyzed by using the ASEP/MD (averaged solvent electrostatic potential from molecular dynamics) method. With this purpose, four molecules, two polar (acrolein and formaldehyde) and two non-polar (p-difluorobenzene and trans-difluoroethene) have been studied in solvents of diverse polarity. Independently of the nature of the system we found that the contribution of SSE on the average value of the solvent shift or on the multipole moment values is negligible. In the case of centro-symmetric molecules, our results permit to discard the SSE as cause of the solvent shift found, which must be assigned to the electrostatic interaction of the solute quadrupole and higher multipoles with the solvent. As the SSE values provide also a measure of the errors introduced by the mean field approximation (MFA), these results indicate that MFA permits a very accurate determination of the solvent shift at the same time that it reduces drastically the computational cost. Finally, a new procedure suited to the ASEP/MD method has been presented that permits to estimate the inhomogeneous broadening of spectral bands, complementing the information provided by mean field theories. This procedure does not need additional quantum calculations and its computational cost is minimal.

Keywords

Solvent Stark effect ASEP/MD QM/MM Mean field theories 

Notes

Acknowledgments

This work was supported by the CTQ2008-06224 Project from the Ministerio de Ciencia e Innovación of Spain and the PRI08A056 Project from the Consejería de Economía, Comercio e Innovación of the Junta de Extremadura.

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Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  • M. Elena Martín
    • 1
  • M. Luz Sánchez
    • 1
  • José C. Corchado
    • 1
  • Aurora Muñoz-Losa
    • 1
  • Ignacio Fdez. Galván
    • 1
  • Francisco J. Olivares del Valle
    • 1
  • Manuel A. Aguilar
    • 1
  1. 1.Química Física, Edif. José María Viguera LoboUniversidad de ExtremaduraBadajozSpain

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