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在本文中,我们将介绍运用第一性原理计算包含非谐效应或势能面锥形交叉情况下内转换速率的最新工作。我们同时计算了包含非谐效应的分子吸收和发射光谱,以检验量子化学方法计算得到势能面的准确性。势能面的锥形交叉对内转换过程的影响是学界广泛关注的焦点。本文将介绍如何在内转换速率计算的过程中考虑势能面锥形交叉的影响,并将之运用于吡嗪分子。本文运用绝热近似理论处理了另外一个重要的无辐射过程,分子的振动驰豫过程,并将这个理论应用于水二聚体和苯胺的振动弛豫速率的计算。
In this article, we describe the most recent work in using first principles to calculate the internal slew rates with anharmonic or taper crossings of potential energy surfaces. We also calculate molecular absorption and emission spectra that include anharmonic effects to verify the accuracy of the potential energy surface calculated by quantum chemistry. The influence of the cone cross on the transition process of the potential energy surface is the focus of the academic community. This article describes how to consider the influence of the conical intersection of the potential energy surface in the calculation of the internal conversion rate and apply it to the pyrazine molecule. In this paper, we use the adiabatic approximation theory to deal with another important non-radiation process and molecular vibration relaxation process, and apply this theory to the calculation of the vibration relaxation rate of water dimer and aniline.