Moiseyev Nimrod
Schulich Faculty of Chemistry and Faculty of Physics, Technion-Israel Institute of Technology, Haifa 32000, Israel.
J Phys Chem A. 2009 Jul 2;113(26):7660-6. doi: 10.1021/jp8110925.
As has been shown long time ago by Feshbach, the exact energy spectrum of the full problem can be obtained by solving two different self-energy problems. In spite of the fact that the two effective Hamiltonians are derived in very similar ways in one case, the exact energy spectrum of the full problem can be either real or complex (depending on the boundary conditions), whereas the exact energy spectrum associated with the second effective Hamiltonian has to be complex (excluding bound states in the continuum). The focus of this paper is on the fact that in both cases the complex eigenvalues result from the same requirement of an out-going boundary condition. The branching of quantum mechanics to standard (Hermitian) formalism and non-Hermitian formalism is associated with the decision to express the exact energy spectrum with one of the two possible self-consistent like problems where the use of the Green operator imposes an outgoing boundary condition on the solutions of the time-independent Schrodinger equation. Our analysis is made for the case where an ABC molecule has sufficient energy to dissociate to A + BC but not to A + B + C and not to AB + C or to AC + B.
正如费什巴赫很久以前所表明的那样,完整问题的精确能谱可以通过求解两个不同的自能问题得到。尽管在一种情况下,两个有效哈密顿量的推导方式非常相似,但完整问题的精确能谱可以是实的,也可以是复的(取决于边界条件),而与第二个有效哈密顿量相关的精确能谱必定是复的(不包括连续谱中的束缚态)。本文的重点在于,在这两种情况下,复本征值都源于对出射边界条件的相同要求。量子力学向标准(厄米)形式主义和非厄米形式主义的分支,与用两个可能的自洽类问题之一来表示精确能谱的决定相关,其中格林算子的使用对不含时薛定谔方程的解施加了出射边界条件。我们针对ABC分子具有足够能量解离为A + BC,但不能解离为A + B + C、AB + C或AC + B的情况进行分析。