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Development and experimental verification of a theory for high-field, ultralow-temperature magnetic linear dichroism of glasses containing molecular chromophores with spin doublet ground states
1.J. Peterson, L. L. Pearce, and E. L. Bominaar, J. Am. Chem. Soc. 121, 5972 (1999).
2.A. Cotton and H. Mouton, Ann. Chim. Phys. 11, 145 (1907).
3.E. L. Bominaar, C. Achim, and J. Peterson, J. Chem. Phys. 109, 942 (1998).
4.M. Kreglewski and M. Vala, J. Chem. Phys. 74, 5411 (1981).
5.M. Vala, J. C. Rivoal, C. Grisolia, and J. Pyka, J. Chem. Phys. 82, 4376 (1985).
6.M. Vala, M. Eyring, J. Pyka, J. C. Rivoal, and C. Grisolia, J. Chem. Phys. 83, 969 (1985).
7.A. C. Boccara, J. Ferré, B. Briat, M. Billardon, and J. P. Badoz, J. Chem. Phys. 50, 2716 (1969).
8.P. J. Stephens, J. Chem. Phys. 52, 3489 (1970).
9.P. J. Stephens, Annu. Rev. Phys. Chem. 25, 201 (1974).
10.These were termed “diagonal” and “off-diagonal” in Ref. 3.
11.As will be discussed below, this order is found at 4.2 K, using the parameters for ferricytochrome c, and
12.A. Abragam and B. Bleaney, Electron Paramagnetic Resonance of Transition Ions (Dover, New York, 1986).
13.C. Cohen-Tannoudji, B. Diu, and F. Laloë, Quantum Mechanics (Wiley, New York, 1977), p. 984.
14.G. Arfken, Mathematical Methods for Physicists (Academic, New York, 1970), p. 180.
15.M. Gouterman, in The Porphyrins, Physical Chemistry, Part A, edited by D. Dolphin (Academic, New York, 1978), Vol. III, pp. 1–165.
16.This experiment was performed on the sample of Fig. 1, using a field of 4 T. While at 4.2 K the MLD spectrum was clearly detectable, it vanished within the noise when the temperature was increased to 30 K.
17.A. P. Mineyev and Y. A. Sharonov, Theor. Chim. Acta 49, 295 (1978).
18.A. P. Mineyev, Y. A. Sharonov, N. A. Sharonova, Y. P. Lysov, and V. A. Figlovsky, Theor. Chim. Acta 63, 421 (1983).
19.The current equipment was originally assembled primarily with visible-to-near-infrared MCD measurements in mind, then modified for MLD purposes. However, the present configuration of the instrument is unsuitable for making MLD measurements in the Soret region. Consequently, we cannot undertake these studies until such time as some necessary further modification to the instrument has been carried out.
20.The data collection protocol described in Ref. 1 removes spurious MCD contributions to the MLD spectrum, provided the monochromator drive mechanism functions ideally and the signal processing electronics remain stable during the required set of measurements. In practice, neither of these conditions are fully met and any variation in the operating characteristics of these components between measurements performed with the magnetic field applied in the perpendicular and antiperpendicular orientations (see Ref. 1) may result in an incomplete cancellation of the MCD component. The problem is particularly acute in the present set of experiments where the low-spin ferric samples employed exhibit unusually strong MCD while the measured MLD signals are very close to the detection limit. To avoid incomplete cancellation of the MCD component, we have performed the measurements of Fig. 2 on the MLD band that occurs in a spectral region where the MCD (not shown) is weak.
21.This result attests to the correctness of the theorem proved in Sec. II, because if the inner-state, zeroth-derivative term were the dominant MLD effect, the magnetization curve would approach a constant value in the high-field limit, at variance with the observed behavior.
22.M. K. Johnson, E. C. Duin, B. R. Crouse, M. P. Golinelli, and J. Meyer, in Spectroscopic Methods in Bioinorganic Chemistry, edited by E. I. Solomon and K. O. Hodgson (American Chemical Society, Washington, DC, 1998), Vol. 692, pp. 286–301.
23.P. N. Schatz, R. L. Mowery, and E. R. Krausz, Mol. Phys. 35, 1537 (1978).
24.E. I. Solomon, E. G. Pavel, K. E. Loeb, and C. Campochiaro, Coord. Chem. Rev. 144, 369 (1995).
25.In the case of an inner-state Zeeman effect, the magnetization curves collected at different temperatures overlap when plotted versus the reduced parameter in the case of an outer-state effect, these curves are nested.
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