Department of Chemistry, Imperial College, London SW7 2AZ, United Kingdom, and Institut de Quimica, Computational and Departament de Quimica, Universitat de Girona, E-17071 Girona, Spain.
J Chem Theory Comput. 2008 Feb;4(2):257-66. doi: 10.1021/ct7002435.
In this paper we present two new algorithms to study the extended nature of the crossing seam between electronic potential energy surfaces. The first algorithm is designed to optimize conical intersection geometries: both minima and saddle points. In addition, this method will optimize conical intersection geometries using arbitrary geometrical constraints. We demonstrate its potential on different crossing seams of benzene, z-penta-3,5-dieniminium, and 1,3-butadiene. The second algorithm is designed to explicitly compute the intersection-space minimum energy coordinate. Our computations show how an intersection seam and the energy along it can be unambiguously defined. A finite region of the S0/S1 1,3-butadiene crossing seam has been mapped out, and a new saddle point linked with two lower-lying geometries on the seam.
本文提出了两种新算法来研究电子势能面交叉缝的扩展性质。第一种算法旨在优化双锥交叉点的几何形状：既包括极小值点又包括鞍点。此外，该方法还可以使用任意几何约束来优化双锥交叉点的几何形状。我们在苯、z-戊-3,5-二烯亚胺和 1,3-丁二烯的不同交叉缝上展示了它的潜力。第二种算法用于明确计算交叉空间中的最低能量坐标。我们的计算结果表明，如何明确地定义交叉缝及其沿线的能量。我们已经绘制出 S0/S1 1,3-丁二烯交叉缝的一个有限区域，并找到了与缝上两个较低构象相连的新鞍点。
