Quantum Mechanics and Dynamics of Open Polyatomic Systems

我们建议从计算和理论上研究耦合到外部环境的多原子（大）分子系统的光诱导量子动力学的各个方面。这样的系统在化学中无处不在，影响着生活的方方面面。事实上，分子与阳光的相互作用，例如在光合作用中，是能量传递给地球上生命的主要来源。在所有要研究的情况下，我们将继续发展形式理论，并建立包含所研究系统的基本物理化学的模型。当认为有启发时，将调用更复杂的建模。提出的工作是最先进的理论和计算化学，利用最现代化的并行计算机设施。这种研究往往先于技术和工业的发展，使加拿大在重要的先进技术应用方面具有优势。该计划还有望提供对培养现代高素质人才至关重要的研究环境和研究挑战。

We propose to study, both computationally and theoretically, various aspects of light-induced quantum dynamics of polyatomic (large) molecular systems that are coupled to an external environment. Such systems are ubiquitous in Chemistry, affecting all aspects of life. Indeed, the interaction of molecules with sunlight, in photosynthesis for example, is the primary source by which energy is transmitted to life on earth. In all cases to be studied we will proceed by developing formal theories, and building models containing the essential physical chemistry of the system examined. More complex modeling will be invoked when deemed enlightening. The work proposed is state-of-the-art in theoretical and computational chemistry, taking advantage of the most modern of parallel computer facilities. Such research often precedes and heralds developments in technology and industry, providing Canada with the edge in important advanced technological applications. The proposed program is also expected to provide the research environment and research challenges that are vital to the training of modern, highly qualified personnel. In addition to basic issues in light-matter interactions we will consider two major directions: (a) Coherent Control of Dynamic Processes is a foundational approach to controlling molecular processes via quantum interference effects. The methodology, based upon work that we have done over several decades, has been highly successful for small, isolated quantum systems. By contrast, control of larger molecules that are coupled to external environments (e.g., in solution or in a protein matrix) is a fertile field that we propose to explore in detail. The results are expected to significantly expand the range of control over processes in chemistry using quantum interference effects, an emergent technology for the coming century. (b) Open Quantum Systems are described by master equations, which are inherently subject to a wide collection of approximations (secular vs. nonsecular, Markovian vs. Non-Markovian, global vs. local couplings, low order perturbation theories, etc.). The choice of approximation has a profound influence on the resultant dynamics. We propose extensive studies designed to explore domains of validity of these approximate schemes for photosynthetic systems. Of importance here is the actual nature of the coupling between the system and environment, explored using a variety of methods. The results are expected to contribute significantly to the range of validity and applicability of master equation methods for light harvesting processes. In addition, we will examine issues related to the ability of photosynthetic systems to act as photon detectors, an issue of fundamental significance.