Gómez-Carrasco Susana, Aguado Alfredo, Paniagua Miguel, Roncero Octavio
Unidad Asociada UAM-CSIC, Instituto de Matemáticas y Física Fundamental, CSIC, Serrano 123, 28006 Madrid, Spain.
J Chem Phys. 2006 Oct 28;125(16):164321. doi: 10.1063/1.2363988.
An energy-based method is proposed for the diabatization of the OH(2Pi)+F(2P)-->O(3P)+HF(1Sigma+) reaction. It is demonstrated that the diabatic representation obtained is regularized, i.e., the residual derivative couplings do not present singularities at the conical intersections appearing along the reaction path. This method only requires the knowledge of the 1,2 3A" and 1 3A' eigenvalues and does not require any adjustable parameter. Thus, many convergence problems arising in other derivative-based diabatization methods are avoided, and the description of the configuration space along the reaction path is enormously simplified. Three-dimensional coupled diabatic energy surfaces are obtained by an interpolation procedure using approximately 4000 accurate ab initio points. The angular resolved photodetachment cross sections are obtained in the diabatic and adiabatic representations using a wave packet method. An excellent agreement is obtained with recent experimental data [D. M. Neumark, Phys. Chem. Chem. Phys. 7, 433 (2005)] for high electron kinetic energies where only the triplet electronic states contribute.
提出了一种基于能量的方法用于OH(2Pi)+F(2P)-->O(3P)+HF(1Sigma+)反应的非绝热态确定。结果表明，所获得的非绝热表示是正则化的，即残余导数耦合在沿反应路径出现的锥形交叉点处不存在奇点。该方法仅需要知道1,2 3A"和1 3A'本征值，且不需要任何可调参数。因此，避免了其他基于导数的非绝热态确定方法中出现的许多收敛问题，并且极大地简化了沿反应路径的构型空间描述。通过使用大约4000个精确的从头算点的插值程序获得了三维耦合非绝热能量表面。使用波包方法在非绝热和绝热表示中获得了角分辨光剥离截面。对于仅三重态电子态起作用的高电子动能，与最近的实验数据[D. M. Neumark, Phys. Chem. Chem. Phys. 7, 433 (2005)]取得了极好的一致性。
