Orientation of dipole molecules and clusters upon adiabatic entry into an external field
J. Chem. Phys. 129, 024101 (2008); doi:10.1063/1.2946712
Published 8 July 2008
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The induced polarization of a beam of polar clusters or molecules passing through an electric or magnetic field region differs from the textbook Langevin–Debye susceptibility. This distinction, which is important for the interpretation of deflection and focusing experiments, arises because instead of acquiring thermal equilibrium in the field region, the beam ensemble typically enters the field adiabatically, i.e., with a previously fixed distribution of rotational states. We discuss the orientation of rigid symmetric top systems with a body-fixed electric or magnetic dipole moment. The analytical expression for their “adiabatic-entry” orientation is elucidated and compared with exact numerical results for a range of parameters. The differences between the polarization of thermodynamic and “adiabatic-entry” ensembles of prolate and oblate tops, and of symmetric top and linear rotators, are illustrated and identified.
©2008 American Institute of Physics
| History: | Received 6 May 2008; accepted 27 May 2008; published 8 July 2008 |
| Permalink: |
http://link.aip.org/link/?JCPSA6/129/024101/1 |
KEYWORDS and PACS
electric field effects,
electric moments,
magnetic field effects,
magnetic moments,
molecular clusters,
molecular moments,
molecular orientation
- 36.40.Sx
Diffusion and dynamics of atomic and molecular clusters - 33.15.Kr
Molecular electric and magnetic moments (and derivatives), polarizability, and magnetic susceptibility - 33.15.Hp
Molecular barrier heights (internal rotation, inversion, rotational isomerism, conformational dynamics) - YEAR: 2008
RELATED DATABASES
PUBLICATION DATA
0021-9606 (print)
1089-7690 (online)
REFERENCES (43)
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- R. G. J. Fraser, Molecular Beams (Chemical Publishing Co., New York, 1938).
- N. F. Ramsey, Molecular Beams (Oxford University Press, Oxford, 1956).
- Atomic and Molecular Beams Methods, edited by G. Scoles (Oxford University Press, Oxford, 1988).
- H. J. Loesch and A. Remscheid, J. Chem. Phys. 93, 4779 (1990).
- B. Friedrich and D. R. Herschbach,
Z. Phys. D: At., Mol. Clusters 18, 153 (1991) . - S. Stolte, in Atomic and Molecular Beams Methods, edited by G. Scoles (Oxford University Press, Oxford, 1988).
- H.-J. Loesch,
Annu. Rev. Phys. Chem. 46, 555 (1995) . - R. E. Miller,
Proc. SPIE 3271, 151 (1998) . - C. E. Heiner, H. L. Bethlem, and G. Meijer,
Phys. Chem. Chem. Phys. 8, 2666 (2006) . - T. Rieger, T. Junglen, S. A. Rangwala, G. Rempe, P. W. H. Pinkse, and J. Bulthuis, Phys. Rev. A 73, 061402 (2006).
- W. A. de Heer, in Metal Clusters at Surfaces, edited by K.-H. Meiwes-Broer (Springer, Berlin, 2000).
- X. Xu, S. Yin, R. Moro, and W. A. de Heer, Phys. Rev. Lett. 95, 237209 (2005).
- M. Broyer, R. Antoine, E. Benichou, I. Compagnon, Ph. Dugourd, and D. Rayane,
C. R. Phys. 3, 301 (2002) . - M. Schnell, C. Herwig, and J. A. Becker,
Z. Phys. Chem. 217, 1003 (2003) . - M. B. Knickelbein, J. Chem. Phys. 121, 5281 (2004).
- F. W. Payne, W. Jiang, J. W. Emmert, J. Deng, and L. A. Bloomfield, Phys. Rev. B 75, 094431 (2007).
- For a paramagnetic molecule the dipole moment is strongly dependent on the specific quantum state, and an ensemble of rigid linear molecules will display only an average alignment rather than orientation [B. Friedrich and D. R. Herschbach,
Z. Phys. D: At., Mol. Clusters 24, 25 (1992) ]. - P. Langevin, J. Phys. 4, 678 (1905).
- P. Debye, Polar Molecules (Dover, New York, 1945).
- J. H. Van Vleck, The Theory of Electric and Magnetic Susceptibilities (Oxford University Press, London, 1932).
- R. H. Fowler, Statistical Mechanics (Cambridge University Press, Cambridge, 1936).
- The rotational constants A,B,C, are defined as the inverse of the principal moments of inertia, e. g., B=
2/2Ib, and by convention are assigned as A
B
C. - G. F. Bertsch and K. Yabana, Phys. Rev. A 49, 1930 (1994).
- G. F. Bertsch, N. Onishi, and K. Yabana,
Z. Phys. D: At., Mol. Clusters 34, 213 (1995) . - B. Friedrich,
Eur. Phys. J. D 38, 209 (2006) . - S. E. Choi and R. B. Bernstein, J. Chem. Phys. 85, 150 (1986).
- Ph. Dugourd, I. Compagnon, F. Lepine, R. Antoine, D. Rayane, and M. Broyer,
Chem. Phys. Lett. 336, 511 (2001) . - C. H. Townes and A. L. Schawlow, Microwave Spectroscopy (Dover, New York, 1975).
- J. Bulthuis, J. J. van Leuken, and S. Stolte,
J. Chem. Soc., Faraday Trans. 91, 205 (1995) . - B. Friedrich and D. R. Herschbach,
Int. Rev. Phys. Chem. 15, 325 (1996) . - R. de L. Kronig,
Proc. Natl. Acad. Sci. U.S.A. 12, 608 (1926) . - H. J. Loesch and A. Remscheid,
J. Phys. Chem. 95, 8194 (1991) . - The exception with the calculation for CH3I in Ref. 29 was due to an error in the calculation.
- I. Estermann and R. G. J. Fraser, J. Chem. Phys. 1, 390 (1933).
- W. Pauli,
Z. Phys. 6, 319 (1921) . - K. F. Niessen,
Phys. Rev. 34, 253 (1929) . - J. Bulthuis, J. Möller, and H. J. Loesch,
J. Phys. Chem. A 101, 7684 (1997) . - W. Kong and J. Bulthuis,
J. Phys. Chem. A 104, 1055 (2000) . - Ph. Dugourd, R. Antoine, M. Abd El Rahim, D. Rayane, M. Broyer, and F. Calvo,
Chem. Phys. Lett. 423, 13 (2006) . - M. Abd El Rahim, R. Antoine, M. Broyer, D. Rayane, and Ph. Dugourd,
J. Phys. Chem. A 109, 8507 (2005) . - R. Antoine, M. Abd El Rahim, M. Broyer, D. Rayane, and Ph. Dugourd,
J. Phys. Chem. A 110, 10006 (2006) . - V. Visuthikraisee and G. F. Bertsch, Phys. Rev. A 54, 5104 (1996).
- R. Moro, J. Bulthuis, J. Heinrich, and V. V. Kresin, Phys. Rev. A 75, 013415 (2007).








