Theoretical modeling of the formic acid dimer infrared spectrum: Shaping the O–H stretch band (original) (raw)

Abstract

The potential energy surface of the formic acid dimer is investigated in the vicinity of the minima. The linear absorption IR spectrum in the region of the O-H antisymmetric stretch is analyzed using a combination of a second-order perturbative treatment and non-perturbative calculations in reduced dimensionality. The importance of particular coupling mechanisms is studied systematically and it has been shown that the red-shift of the m OH (B u ) center frequency is almost exclusively caused by the Davydov coupling to the symmetric O-H stretching vibration. We find that anharmonic couplings to low frequency dimer stretching and rocking modes, and Fermi resonances to mid-infrared modes contribute to the width, but only in a minor extent to the frequency of the m OH (B u ) band maximum.

Loading...

Loading Preview

Sorry, preview is currently unavailable. You can download the paper by clicking the button above.

References (40)

  1. G.A. Jeffrey, Introduction to Hydrogen Bonding, Oxford University Press, New York, 1997.
  2. D. Hadz ˇi, Theoretical Treatments of Hydrogen Bonding, Wiley, Chichester, 1997.
  3. H.H. Limbach, J. Manz, Hydrogen Transfer: Experiment and Theory, Ber. Bunsenges. Phys. Chem. 102 (1998) (special issue).
  4. G.H. Kwei, R.F. Curl, J. Chem. Phys. 32 (1960) 1592.
  5. A. Almenningen, O. Bastiansen, T. Motzfeld, Acta Chem. Scand. 23 (1969) 2848.
  6. Y. Mare ´chal, J. Chem. Phys. 87 (1987) 6344.
  7. F. Ito, T. Nakanaga, Chem. Phys. Lett. 318 (2000) 571.
  8. F. Ito, T. Nakanaga, Chem. Phys. Lett. 277 (2002) 163.
  9. F. Madeja, M. Havenith, J. Chem. Phys. 117 (2002) 7162.
  10. Y. Mare ´chal, A. Witkowski, J. Chem. Phys. 48 (1968) 3697.
  11. N. Shida, P.F. Barbara, J.E. Almlo ¨f, J. Chem. Phys. 94 (1991) 3633.
  12. T. Neuheuser, B.A. Hess, J. Phys. Chem. 98 (1994) 6459.
  13. M.V. Vener, O. Ku ¨hn, J.M. Bowman, Chem. Phys. Lett. 349 (2001) 562.
  14. C.S. Tautermann, A.F. Voegele, K.R. Liedl, J. Chem. Phys. 120 (2004) 631.
  15. D. Luckhaus, J. Phys. Chem. A 110 (2006) 3151.
  16. Z. Smedarchina, A. Fernandez-Ramos, W. Siebrand, J. Chem. Phys. 122 (2005) 4309.
  17. K. Giese, M. Petkovic ´, H. Naundorf, O. Ku ¨hn, Phys. Rep. 430 (2006) 211.
  18. G.M. Florio, T.S. Zwier, E.M. Myshakin, K.D. Jordan, E.L. Silbert III, J. Chem. Phys. 118 (2003) 1735.
  19. J. Mavri, J. Grdadolnik, J. Phys. Chem. A 105 (2001) 2039.
  20. I. Matanovic ´, N. Dos ˇlic ´, J. Phys. Chem. A 109 (2005) 4185.
  21. P. Blaise, M.J. Wojcik, O. Henri-Rousseau, J. Chem. Phys. 122 (2005) 064306.
  22. J. Dreyer, J. Chem. Phys. 122 (2005) 184306.
  23. V. Barone, J. Chem. Phys. 120 (2004) 3059.
  24. V. Barone, J. Chem. Phys. 122 (2005) 014108.
  25. I. Matanovic ´, N. Dos ˇlic ´, Int. J. Quantum Chem. 106 (2006) 1367.
  26. J. Antony, G. von Helden, G. Meijer, B. Schmidt, J. Chem. Phys. 123 (2005) 014305.
  27. A.D. Becke, J. Chem. Phys. 98 (1993) 5648.
  28. M.J. Frisch et al., Gaussian 03, Revision B.05, Gaussian, Inc., Pittsburgh PA, 2003.
  29. N. Dos ˇlic ´, O. Ku ¨hn, Z. Phys. Chem. 217 (2003) 1507.
  30. R.J. Renka, ACM Trans. Math. Software 14 (1988) 151.
  31. C.C. Marston, G. Balint-Kurti, J. Chem. Phys. 91 (1989) 3571.
  32. J. Stare, G.G. Balint-Kurti, J. Phys. Chem. 107 (2003) 7204.
  33. G.H. Golub, C.F.V. Loan, Matrix Computations, The Johns Hopkins University Press, Baltimore, 1985.
  34. D. Sorensen, Tutorial: Implicitly Restarted Arnoldi/Lanczos Meth- ods for Large Scale Eigenvalue Calculations, Rice University, Houston, 1995.
  35. R.B. Lehoucq, D. Sorensen, C.D. Yang, ARPACK User's Guide: Solution of Large Scale Eigenvalue Problems with Implicitly Restarted Arnoldi Methods, Rice University, Houston, 1997.
  36. S. Simon, M. Duran, J.J. Dannenberg, J. Chem. Phys. 105 (1996) 11024.
  37. S.F. Boys, F. Bernardi, Mol. Phys. 19 (1970) 553.
  38. K. Heyne, N. Huse, E. Nibbering, T. Elsaesser, Chem. Phys. Lett. 369 (2003) 591.
  39. K. Heyne, N. Huse, E. Nibbering, T. Elsaesser, Chem. Phys. Lett. 382 (2003) 19.
  40. Landoldt-Bo ¨rnstein, Structure data of free polyatomic moleculesNew series, vol. II/7, Springer, Berlin, 1976.