The thermal spin transition in the diluted mixed crystal is studied at 1 bar and 1 kbar by temperature-dependent absorption spectroscopy. From thermodynamic analysis of the high-spin (HS) fractions, values for and of 1551(50) cm−1 and 7.5(5) cm−1/K and a molecular volume of reaction, of 22(2) Å3 result. Reconsideration of the cooperative effects in the neat from Adler et al. [Hyperfine Interact. 47, 343 (1989)] result in a lattice shift, Δ, of 208(15) cm−1 and an interaction constant, Γ, of 109(15) cm−1. Temperature-dependent laser flash photolysis experiments in the spin-crossover system and the LS system in the pressure range between 1 bar and 1 kbar are presented. Above ≈100 K the (low-spin) relaxations behave classically, whereas they become almost temperature independent below 50 K. At ambient pressure, the low-temperature tunneling rate constant in is more than three orders of magnitude larger than the one in External pressure of 27 kbar accelerates the low-temperature tunneling process by almost nine orders of magnitude. The kinetic results are discussed within the theory of nonadiabatic multiphonon relaxation.
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8 December 1998
Research Article|
December 08 1998
relaxation in
Sabine Schenker;
Sabine Schenker
Département de Chimie Physique, Université de Genève, 30 quai Ernest-Ansermet, 1211 Genève 4, Switzerland
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Andreas Hauser;
Andreas Hauser
Département de Chimie Physique, Université de Genève, 30 quai Ernest-Ansermet, 1211 Genève 4, Switzerland
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Wei Wang;
Wei Wang
Department of Chemistry, Brandeis University, Waltham, Massachusetts 02254-9110
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I. Y. Chan
I. Y. Chan
Department of Chemistry, Brandeis University, Waltham, Massachusetts 02254-9110
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J. Chem. Phys. 109, 9870–9878 (1998)
Article history
Received:
April 06 1998
Accepted:
August 31 1998
Citation
Sabine Schenker, Andreas Hauser, Wei Wang, I. Y. Chan; relaxation in . J. Chem. Phys. 8 December 1998; 109 (22): 9870–9878. https://doi.org/10.1063/1.477681
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