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Coherent control of molecular dissociation in ultrafast strong fields has received considerable attention in various scientific disciplines, such as atomic and molecular physics, physical chemistry, and quantum control. Many fundamental issues still exist regarding the understanding of phenomena, exploration of mechanisms, and development of control strategies. Recent progress has shown that manipulating the spectral phase distribution of a single ultrafast strong ultraviolet laser pulse while maintaining the same spectral amplitude distribution can effectively control the total dissociation probability and branching ratio of molecules initially in the ground state. In this work, the spectral phase control of the photodissociation reaction of chlorobromomethane (CH2BrCl) is studied in depth by using a time-dependent quantum wave packet method, focusing on the influence of the initial vibrational state on the dissociation reaction. The results show that modifying the spectral phase of a single ultrafast pulse does not influence the total dissociation probability or branching ratio in the weak field limit. However, these factors exhibit significant dependence on the spectral phase of the single ultrafast pulse in the strong field limit. By analyzing the population distribution of vibrational states in the ground electronic state, we observe that chirped pulses can effectively control the resonance Raman scattering (RRS) phenomenon induced in strong fields, thereby selectively affecting the dissociation probability and branching ratio based on initial vibrational states. Furthermore, we demonstrate that by selecting an appropriate initial vibration state and controlling both the value and sign of the chirp rate, it is possible to achieve preferential cleavage of Cl+CH2Br bonds. This study provides new insights into understanding of ultrafast coherent control of photodissociation reactions in polyatomic molecules.
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Keywords:
- photodissociation /
- coherent control /
- initial vibrational states /
- resonance Raman scattering
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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^{{\mathrm{di}}} $和$ V_2^{{\mathrm{di}}} $
Figure 1. Schematic illustration of laser control in the photodissociation process of $ \rm {CH_{2}BrCl} $. (a) The model showcasing 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) Photodissociation channel along the Br—CH2 reaction coordinate for different initial vibrational states $ |\nu'\nu''\rangle $. (c) The channel along the Cl—CH2 reaction coordinate for the same initial states $ |\nu'\nu''\rangle $. The black, red, and blue solid lines represent the adiabatic potential energy curves of ground electronic state $ \text{S}_0(V_0^\text{ad}) $, the first excited electronic state $ \text{S}_1(V_1^\text{ad}) $, and the second excited electronic state $ \text{S}_2(V_2^\text{ad}) $, respectively. Notably, the red-dashed line and the black-dashed line represent the non-adiabatic potential $ V_1^{\mathrm{di}} $ and $ V_2^{\text{di}} $.
图 2 CH2BrCl分子初始振动态为$ |00\rangle $, $ |10\rangle $和$ |20\rangle $时, (a)—(c)基电子态的二维振动本征函数密度分布; (d)—(f)弱场极限下Br+CH2Cl通道和Cl+CH2Br通道的含时解离概率(分别用$ 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概率, (m)—(o)相应的含时解离分支比
Figure 2. For the initial vibrational states of $ |00\rangle $, $ |01\rangle $ and $ |02\rangle $, (a)–(c) two-dimensional vibrational eigenfunction density distributions; (d)–(f) the dissociation probabilities of Br+CH2Cl and Cl+CH2Br channels in the weak-field limit (marked with $ P^{\mathrm{Br}} $ and $ P^{\mathrm{Cl}} $, respectively), and (g)–(i) the corresponding time-dependent dissociation branching ratios R; (j)–(l) and (m)–(o) as well as in the strong-field limit.
图 3 CH2BrCl分子初始振动态为$ |01\rangle $, $ |02\rangle $和$ |11\rangle $时, (a)—(c)基电子态的二维振动本征函数密度分布; (d)—(f)弱场极限下Br+CH2Cl通道和Cl+CH2Br通道的含时解离概率(分别用$ 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概率, (m)—(o)相应的含时解离分支比
Figure 3. For the initial vibrational states of $ |00\rangle $, $ |01\rangle $ and $ |02\rangle $, (a)–(c) two-dimensional vibrational eigenfunction density distributions; (d)–(f) the dissociation probabilities of Br+CH2Cl and Cl+CH2Br channels in the weak-field limit (marked with $ P^{\mathrm{Br}} $ and $ P^{\mathrm{Cl}} $, respectively), and (g)–(i) the corresponding time-dependent dissociation branching ratios R; (j)–(l) and (m)–(o) as well as in the strong-field limit.
图 4 弱场极限下CH2BrCl分子总解离概率(a)—(f)和分支比(g)—(l)作为啁啾率$ \beta_{0} $和不同初始振动态$ |\nu'\nu''\rangle $的函数
Figure 4. Dependence of (a)−(f) total dissociation probability and (g)−(l) branching ratio of CH2BrCl on the chirp rate $ \beta_{0} $ and different initial state $ |\nu'\nu''\rangle $ in the weak-field limit.
图 5 强场极限下, CH2BrCl分子总解离概率(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
Figure 5. (a)–(f) Total dissociation probability and (g)–(l) branching ratio in CH2BrCl as a function of chirp rate $ \beta_{0} $ and different initial state $ |\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_{\mathrm{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_{\mathrm{f}}) $的最大值都出现在$ \beta_0=0 $附近
Figure 6. (a)–(f) Sum of the remaining vibrational states populations $ P(t_{\mathrm{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_{\mathrm{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
Figure 7. 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} $
Figure 8. Resonance Raman scattering phenomenon of the vibrational states of the ground electronic state induced by a chirped pulse in the strong-field limit. For the initial vibrational states of $ |00\rangle $, $ |10\rangle $ and $ |20\rangle $, (a)–(i) the time-dependent populations of the initial state $ P_{\nu'\nu''} $, the total of remaining vibrational states of the ground electronic state $ P(t) $, and the two excited electronic states $ P_{1} $ and $ P_{2} $ with 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} $
Figure 9. Resonance Raman scattering phenomenon of the vibrational states of the ground electronic state induced by a chirped pulse in the strong-field limit. For the initial vibrational states of $ |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 the two excited electronic states $ P_{1} $ and $ P_{2} $ with three different chirp rates $ \beta_0=0 $, $ \pm30 $ fs2.
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[4] Sun Z, Wang C, Zhao W, Yang C 2018 J. Chem. Phys. 149 224307Google Scholar
[5] Yang J, Zhu X, Wolf T J, Li Z, Nunes J P F, Coffee R, Cryan J P, Gühr M, Hegazy K, Heinz T F, Jobe K, Li R, Shen X, Veccione T, Weathersby S, Wilkin K J, Yoneda C, Zheng Q, Martinez T J, Centurion M, Wang X 2018 Science 361 64Google Scholar
[6] Sun Z, Liu Y 2023 Phys. Chem. Chem. Phys. 25 17397Google Scholar
[7] Rubio-Lago L, Chicharro D V, Poullain S M, Zanchet A, Koumarianou G, Glodic P, Samartzis P C, García-Vela A, Bañares L 2023 Phys. Chem. Chem. Phys. 25 11684Google Scholar
[8] Kranabetter L, Kristensen H H, Ghazaryan A, Schouder C A, Chatterley A S, Janssen P, Jensen F, Zillich R E, Lemeshko M, Stapelfeldt H 2023 Phys. Rev. Lett. 131 053201Google Scholar
[9] Lian Z, Hu Z, Qi H, Fei D, Luo S, Chen Z, Shu C C 2021 Phys. Rev. A 104 053105Google Scholar
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[11] Zhang H, Lavorel B, Billard F, Hartmann J M, Hertz E, Faucher O, Ma J, Wu J, Gershnabel E, Prior Y, Averbukh I S 2019 Phys. Rev. Lett. 122 193401Google Scholar
[12] Hong Q Q, Fan L B, Shu C C, Henriksen N E 2021 Phys. Rev. A 104 013108Google Scholar
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Luo S Z, Chen Z, Li X K, Hu Z, Ding D J 2019 Acta Opt. Sin. 39 0126007Google Scholar
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[38] Liebel M, Kukura P 2017 Nat. Chem. 9 45Google Scholar
[39] Wilma K, Shu C C, Scherf U, Hildner R 2018 J. Am. Chem. Soc. 140 15329Google Scholar
[40] Morichika I, Murata K, Sakurai A, Ishii K, Ashihara S 2019 Nat. Commun. 10 3893Google Scholar
[41] Csehi A, Halász G J, Cederbaum L S, Vibók Á 2016 J. Chem. Phys. 144 074309Google Scholar
[42] Tiwari A K, Henriksen N E 2016 J. Chem. Phys. 144 014306Google Scholar
[43] Sun Z, Wang C, Zhao W, Zheng Y, Yang C 2018 Phys. Chem. Chem. Phys. 20 20957Google Scholar
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