To study the O- and Cl-loss dissociations of the ClOO radical, we calculate, under $C_s$ or $C_{\infty v}$ symmetry, the O- and Cl-loss dissociation potential energy curves (PECs) from ten lower-lying states of ClOO at the multiconfigurational second-order perturbation theory (CASPT2) level. To further consider the nonadiabatic process, minimum-energy crossing point (MECP) between potential energy surfaces is optimized at the complete active space self-consistent-field (CASSCF) level. Since the spin-orbital coupling at located $2{}^2\mathrm{\Pi }/1{}^4{\mathrm{\Sigma }}^{+}$ MECP is calculated being zero, the nonadiabatic process in ClOO dissociations involved in this MECP are forbidden. Based on these results, we predict the O- and Cl-loss dissociation mechanisms of ClOO are direct since the excited states are unbounded. Moreover, we propose a new isomerization mechanism between OClO and ClOO, that is, OClO ($\stackrel{\sim }{X}{}^2{B}_1$) $\to$OClO ($\stackrel{\sim }{A}{}^2{A}_2$) $\to$ClOO ($2{}^{2}A\prime \prime$) $\to$ClOO ($\stackrel{\sim }{X}{}^{2}A\prime \prime$), in which less nonadiabatic processes are involved.

为了研究ClOO自由基的O和Cl损失解离，我们计算出 $C_s$ 或者 $C_{\infty v}$对称性，在多构型二阶摄动理论（CASPT2）水平上，ClOO的十个较低态的O和Cl损失解离势能曲线（PEC）。为了进一步考虑非绝热过程，在完整的活动空间自洽场（CASSCF）级别上优化了势能面之间的最小能量交叉点（MECP）。由于自旋轨道耦合位于$\mathrm{2个}{}^{\mathrm{2个}}\mathrm{\Pi }/\mathrm{1个}{}^4{\mathrm{\Sigma }}^{+}$MECP被计算为零，该MECP中涉及的C10解离中的非绝热过程被禁止。基于这些结果，我们预测ClOO的O-和Cl-损失解离机理是直接的，因为激发态是无界的。此外，我们提出了OClO和ClOO之间的一种新的异构化机制，即OClO（$\stackrel{〜}{X}{}^{\mathrm{2个}}{乙}_{\mathrm{1个}}$） $\to$OClO（$\stackrel{〜}{\mathrm{一个}}{}^{\mathrm{2个}}{\mathrm{一个}}_{\mathrm{2个}}$） $\to$克劳（$\mathrm{2个}{}^{\mathrm{2个}}\mathrm{一个}\prime \prime$） $\to$克劳（$\stackrel{〜}{X}{}^{\mathrm{2个}}\mathrm{一个}\prime \prime$），其中涉及的非绝热过程较少。