Quantum chemical construction of a reduced reaction Hamiltonian and T1-relaxation and pure T2-dephasing rates for the proton transfer in 3-chlorotropolone
Quantum chemical construction of a reduced reaction Hamiltonian and T1-relaxation and pure T2-dephasing rates for the proton transfer in 3-chlorotropolone
复制标题
3-氯托酚酮中质子转移的还原反应哈密顿量和 T1 弛豫以及纯 T2 相移速率的量子化学构建
DOI：
10.1140/epjd/e20020082
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发表时间：
2002
期刊：
影响因子：
--
通讯作者：
Oliver Kühn
中科院分区：
文献类型：
--
作者：
R. Xu;Y. J. Yan;Oliver Kühn
将多维问题分解为与谐振子池耦合的相关系统的问题是凝聚相理论中的一个常见概念。针对一个孤立的环庚三烯酚酮衍生物的分子内质子转移的具体问题，我们认为在分子的平面内移动的反应性质子作为系统和其余的基板正常模式作为浴。利用密度泛函理论构造了一个全笛卡尔系统加衬底的哈密顿量。然后，它被用来确定温度依赖的有效约化反应哈密顿量和状态到状态的耗散率诱导vibrillation系统基板耦合到双二次。重要的基板模式的T1-松弛和纯T2-退相速率，这是无论是内部或间井的性质，确定数值和物理分析与分子的细节。
Separating multidimensional problems into that of a relevant system which is coupled to a bath of harmonic oscillators is a common concept in condensed phase theory. Focusing on the specific problem of intramolecular proton transfer in an isolated tropolone derivative, we consider the reactive proton moving in the plane of the molecule as the system and the remaining substrate normal modes as the bath. An all-Cartesian system-plus-substrate Hamiltonian is constructed employing density functional theory. It is then used to determine the temperature-dependent effective reduced reaction Hamiltonian and the state-to-state dissipation rates inducedviathe system-substrate coupling up to the bi-quadratic order. The important substrate modes for the T1-relaxation and the pure T2-dephasing rates, which are either intra- or inter-well in nature, are identified numerically and analyzed physically with molecular details.