图 1  $ \rm {CH_{2}BrCl} $光解离激光控制示意图　(a) 基电子态$ \text{S}_0(\text{a}^{1}\text{A}') $, 激发态$ \text{S}_1(\text{a}^{1}\text{A}') $和$ \text{S}_2(\text{a}^{1}\text{A}') $的光解离动力学模型. (b) 不同初始振动态$ |\nu'\nu''\rangle $沿着Br-CH₂反应坐标描绘的光解离通道. (c) 不同初始振动态$ |\nu'\nu''\rangle $沿Cl-CH₂反应坐标的光解离通道. 其中黑色线、红色线和蓝色线分别表示基电子态$ \text{S}_0(V_0^\text{ad}) $、第一激发电子态$ \text{S}_1(V_1^\text{ad}) $和第二激发电子态$ \text{S}_2(V_2^\text{ad}) $的绝热势能曲线, 红色虚线和黑色虚线分别表示非绝热势能曲线$ V_1^{di} $和$ V_2^{di} $

Fig. 1.  Schematic illustration of laser control in the photodissociation process of $ \rm {CH_{2}BrCl} $. (a) The model showcases the photodissociation dynamics involving the ground electronic state $ \text{S}_0(\text{a}^{1}\text{A}') $, as well as the excited adiabatic electronic states $ \text{S}_1(\text{b}^{1}\text{A}') $ and $ \text{S}_2(\text{c}^{1}\text{A}') $. (b) depict the photodissociation channel along the Br-CH₂ reaction coordinate for different initial vibrational states $ |\nu'\nu''\rangle $, while (c) illustrate the channel along the Cl-CH₂ reaction coordinate for the same initial states $ |\nu'\nu''\rangle $. Where the black, red, and blue lines represent the adiabatic potential energy curves of ground electronic state $ \text{S}_0(V_0^\text{ad}) $, the first excited electronic state excited state $ \text{S}_1(V_1^\text{ad}) $, and the second excited electronic state $ \text{S}_2(V_2^\text{ad}) $, respectively, with the red dashed line representing $ (V_1^{di}) $ and the black dashed line representing $ (V_2^\text{ad}) $.

图 2  CH₂BrCl分子初始振动态为$ |00\rangle $、$ |10\rangle $和$ |20\rangle $时　(a)—(c) 基电子态的二维振动本征函数密度分布; (d)—(f) 弱场极限下Br+CH₂Cl通道和Cl+CH₂Br通道的含时解离几率(分别用$ P^{\mathrm{Br}} $和$ P^{\mathrm{Cl}} $标记), (g)—(i)相应的含时分支比R; (j)—(l) 强场极限下Br+CH₂Cl和Cl+CH₂Br两个通道的含时解离几率, (m)—(o)相应的含时解离分支比

Fig. 2.  For the initial vibrational states are $ |00\rangle $, $ |01\rangle $ and $ |02\rangle $, (a)–(c) Two-dimensional vibrational eigenfunction density distributions; (d)–(f) the dissociation probability plotted as a function of time of Br+CH₂Cl and Cl+CH₂Br channels in the weak-field limit (marked with $ P^{\mathrm{Br}} $ and $ P^{\mathrm{Cl}} $, respectively), Corresponding time-dependent dissociation branching ratios R are shown (g)–(i); (j)–(l) and (m)–(o) as well as in the strong-field limit.

图 3  CH₂BrCl分子初始振动态为$ |01\rangle $、$ |02\rangle $和$ |11\rangle $时　(a)—(c) 基电子态的二维振动本征函数密度分布; (d)—(f) 弱场极限下Br+CH₂Cl通道和Cl+CH₂Br通道的含时解离几率(分别用$ P^{\mathrm{Br}} $和$ P^{\mathrm{Cl}} $标记), (g)—(i)相应的含时分支比R; (j)—(l) 强场极限下Br+CH₂Cl和Cl+CH₂Br两个通道的含时解离几率, (m)—(o)相应的含时解离分支比

Fig. 3.  For the initial vibrational states are $ |00\rangle $, $ |01\rangle $ and $ |02\rangle $, (a)–(c) Two-dimensional vibrational eigenfunction density distributions; (d)–(f) the dissociation probability plotted as a function of time of Br+CH₂Cl and Cl+CH₂Br channels in the weak-field limit (marked with $ P^{\mathrm{Br}} $ and $ P^{\mathrm{Cl}} $, respectively), Corresponding time-dependent dissociation branching ratios R are shown (g)–(i); (j)–(l) and (m)–(o) as well as in the strong-field limit.

图 4  弱场极限下CH₂BrCl分子总解离几率(a)—(f)和分支比(g)—(l)作为啁啾率$ \beta_{0} $和不同初始振动态$ |\nu'\nu''\rangle $的函数

Fig. 4.  Dependence of total dissociation probability and branching ratio in CH₂BrCl as a function of chirp rate $ \beta_{0} $ and $ |\nu'\nu''\rangle $ in the weak-field limit.

图 5  强场极限下, CH₂BrCl分子总解离几率(a)—(f)和分支比(g)—(l)作为啁啾率$ \beta_{0} $和不同初始振动态$ |\nu'\nu''\rangle $的函数

Fig. 5.  (a)–(f) The total dissociation probability and (g)–(l) branching ratio in CH₂BrCl as a function of chirp rate $ \beta_{0} $ and $ |\nu'\nu''\rangle $ in the strong-field limit.

图 6  (a) $ |00\rangle $、(b) $ |10\rangle $、(c) $ |20\rangle $、(d) $ |01\rangle $、(e) $ |02\rangle $、(f) $ |11\rangle $分别作为初始振动态时, 基电子态其余振动态末态布居之和$ P(t_f) $随啁啾率$ \beta_{0} $的变化行为. 对于所有不同的初始振动态, $ P(t_f) $的最大值都出现在$ \beta_0=0 $附近

Fig. 6.  (a)-(f) The sum of the remaining vibrational states populations $ P(t_f) $ of the ground electronic state for the initial vibrational state (a) $ |00\rangle $, (b) $ |10\rangle $, (c) $ |20\rangle $, (d) $ |01\rangle $, (e) $ |02\rangle $ and (f) $ |11\rangle $ as a function of $ \beta_0 $, respectively. The maximum of $ P(t_f) $ appears near $ \beta_0=0 $ for all different initial vibrational states.

图 7  随着啁啾率$ \beta_{0} $的改变, (a) $ |00\rangle $、(b) $ |10\rangle $、(c) $ |20\rangle $、(d) $ |01\rangle $、(e) $ |02\rangle $、(f) $ |11\rangle $分别作为初始振动态时, 基电子态不同振动态$ |\nu'\nu''\rangle $的末态布居分布

Fig. 7.  The final population distributions of different vibrational states $ |\nu'\nu''\rangle $ for the different initial vibrational state (a) $ |00\rangle $, (b) $ |10\rangle $, (c) $ |20\rangle $, (d) $ |01\rangle $, (e) $ |02\rangle $ and (f) $ |11\rangle $, varying with the chirp rate $ \beta_0 $.

图 8  强场极限下啁啾脉冲诱导的基电子态振动态共振拉曼散射现象. 初始振动态为$ |00\rangle $、$ |10\rangle $和$ |20\rangle $时, (a)—(i)啁啾率$ \beta_0=0 $, $ \pm30 $ fs²时的初态含时布居$ P_{\nu'\nu''} $、基电子态其余振动态布居之和$ P(t) $、两个激发电子态的含时布居$ P_{1} $和$ P_{2} $

Fig. 8.  Resonance Raman scattering to the vibrational states of the ground electronic state induced by a strong chirped pulse in the strong-field limit. For the initial vibrational states are $ |00\rangle $, $ |10\rangle $ and $ |20\rangle $, (a)–(i) The time-dependent populations of the initial state $ P_{\nu'\nu''} $, the total of the remaining vibrational states of the ground electronic state $ P(t) $, and two excited electronic states $ P_{1} $ and $ P_{2} $ for three different chirp rates $ \beta_0=0 $, $ \pm30 $ fs².

图 9  强场极限下啁啾脉冲诱导的基电子态振动态共振拉曼散射现象. 初始振动态为$ |01\rangle $、$ |02\rangle $和$ |11\rangle $时, (a)—(i)啁啾率$ \beta_0=0 $, $ \pm30 $ fs²时的初态含时布居$ P_{\nu'\nu''} $、基电子态其余振动态布居之和$ P(t) $、两个激发电子态的含时布居$ P_{1} $和$ P_{2} $

Fig. 9.  Resonance Raman scattering to the vibrational states of the ground electronic state induced by a strong chirped pulse in the strong-field limit. For the initial vibrational states are $ |01\rangle $, $ |02\rangle $ and $ |11\rangle $, (a)–(i) The time-dependent populations of the initial state $ P_{\nu'\nu''} $, the total of the remaining vibrational states of the ground electronic state $ P(t) $, and two excited electronic states $ P_{1} $ and $ P_{2} $ for three different chirp rates $ \beta_0=0 $, $ \pm30 $ fs².