Renge Indrek
Institute of Physics, University of Tartu, EE51014 Tartu, Estonia.
J Chem Phys. 2007 Jul 21;127(3):034504. doi: 10.1063/1.2751170.
Expressions are derived for inhomogeneous band shapes of impurity spectra in highly compressed glassy matrices. Intermolecular guest-host interactions are approximated to isotropic two-body Lennard-Jones 6-12 potentials having different parameters in the ground state and the excited state. Calculated shifts and widths are compared to published values for the absorption spectra of phenanthrene, anthracene [B. Y. Okamoto and H. G. Drickamer, J. Chem. Phys. 61, 2870 (1974)], and several polymethine dyes [G. A. Samara et al., J. Chem. Phys. 37, 1482 (1962)] embedded in polymer hosts and subject to pressures up to 140 kbars. The magnitudes of barochromic shifts of the band maxima and the inhomogeneous broadening suggest that the equilibrium coordinates of the excited state are typically less by 5+/-2%.
推导了高度压缩玻璃态基质中杂质光谱非均匀能带形状的表达式。分子间客体-主体相互作用近似为在基态和激发态具有不同参数的各向同性两体 Lennard-Jones 6-12 势。将计算得到的位移和宽度与已发表的关于嵌入聚合物主体中并承受高达 140 千巴压力的菲、蒽 [B. Y. 冈本和 H. G. 德里卡默，《化学物理杂志》61, 2870 (1974)] 以及几种聚甲炔染料 [G. A. 萨马拉等人，《化学物理杂志》37, 1482 (1962)] 的吸收光谱值进行了比较。能带最大值的压致变色位移幅度和非均匀展宽表明，激发态的平衡坐标通常小 5±2%。
