Microscopic theory of cooperative spin crossover: Interaction of molecular modes with phonons

In this article, we present a new microscopic theoretical approach to the description of spin crossover in molecular crystals. The spin crossover crystals under consideration are composed of molecular fragments formed by the spin-crossover metal ion and its nearest ligand surrounding and exhibiting well defined localized (molecular) vibrations. As distinguished from the previous models of this phenomenon, the developed approach takes into account the interaction of spin-crossover ions not only with the phonons but also a strong coupling of the electronic shells with molecular modes. This leads to an effective coupling of the local modes with phonons which is shown to be responsible for the cooperative spin transition accompanied by the structural reorganization. The transition is characterized by the two order parameters representing the mean values of the products of electronic diagonal matrices and the coordinates of the local modes for the high- and low-spin states of the spin crossover complex. Finally, we demonstrate that the approach provides a reasonable explanation of the observed spin transition in the [Fe(ptz)6](BF4)2 crystal. The theory well reproduces the observed abrupt low-spin → high-spin transition and the temperature dependence of the high-spin fraction in a wide temperature range as well as the pronounced hysteresis loop. At the same time within the limiting approximations adopted in the developed model, the evaluated high-spin fraction vs. T shows that the cooperative spin-lattice transition proves to be incomplete in the sense that the high-spin fraction does not reach its maximum value at high temperature.

Biotic responses to rapid climatic changes

Qualitative and quantitative changes in fossil flora and fauna have been used in many studies to infer climatic change. Here we ask a different question: how do flora and fauna respond to climatic changes such as rapid warming or cooling? As an independent proxy for paleotemperature we take the ratio of oxygen isotopes in biogenically precipitated lake marl and in ostracod shells. This introductory paper describes the project design and the five sites on an altitudinal transect from 600 m to about 2300 m asl in the western Swiss Alps. As cases of climatic cooling and warming we use the beginning and end of the Younger Dryas as major changes, and the Gerzensee and Preboreal oscillations as minor changes. At the two sites of Gerzensee and Leysin these changes are recorded in stable-isotope ratios, and there the time scales can be derived by correlations to the GRIP ice core (Schwander et al., 2000 and von Grafenstein et al., 2000). Biotic responses to climate changes are treated in individual papers using pollen (Wick, 2000), plant macrofossils (Tobolski and Ammann, 2000), and remains of chironomids (Brooks, 2000), beetles and other insects (Lemdahl, 2000), and chydorid Cladocera (Hofmann, 2000). They are followed by a synthesis focusing on quantification of biotic responses (Ammann et al., 2000). In addition, a reconstruction of summer temperatures for the Allerød and the Younger Dryas at Gerzensee is provided by Lotter et al. (2000).