Lin Guang-Shuang-Mu, Xie Changjian, Xie Daiqian
Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210093, China.
Department of Chemistry and Chemical Biology, University of New Mexico , Albuquerque, New Mexico 87131, United States.
J Phys Chem A. 2017 Nov 9;121(44):8432-8439. doi: 10.1021/acs.jpca.7b09070. Epub 2017 Oct 30.
New reduced three-dimensional (3D) diabatic potential energy surfaces (PESs) involving the ππ, ππ*, and πσ* states for the nonadiabatic photodissociation CHSH(S) + hv → CHSH(ππ*/πσ*) → H + CHS•(A/X) were constructed at a high computational level, namely explicitly correlated multireference configuration interaction (MRCI-F12) method with the cc-pVTZ-F12 basis. The diabatization of the PESs was achieved by a simple, efficient, and reliable "regularized diabatization" method [Köppel, H.; Gronki, J.; Mahapatra, S. J. Chem. Phys. 2001, 115, 2377-2388]. The dissociation energy of the S state and the excitation energies of the excited S and S states were found to be in reasonably good agreement with the experimental values. The vibronic energy levels of the thiophenol (PhSH) and deuterated thiophenol (PhSD) for S and S states were calculated using a three-dimensional model, and they are in reasonably good agreement with the available experimental results, which validate the high accuracy of the adiabatic PESs and the reasonability of the diabatic couplings.
利用高精度计算方法，即采用cc-pVTZ-F12基组的显式相关多参考组态相互作用（MRCI-F12）方法，构建了涉及非绝热光解离CHSH(S) + hv → CHSH(ππ*/πσ*) → H + CHS•(A/X)过程中ππ、ππ和πσ态的新的简化三维（3D）非绝热势能面（PESs）。通过一种简单、高效且可靠的“正则化 diabatic 化”方法[Köppel, H.; Gronki, J.; Mahapatra, S. J. Chem. Phys. 2001, 115, 2377 - 2388]实现了PESs的 diabatic 化。发现S态的解离能以及激发态S和S的激发能与实验值相当吻合。使用三维模型计算了硫酚（PhSH）和氘代硫酚（PhSD）在S和S态的振转能级，它们与现有的实验结果相当吻合，这验证了绝热PESs的高精度以及 diabatic 耦合的合理性。
