Bertrand Retail

Adiabatic and nonadiabatic dynamics in the CH3(CD3)+HCl reaction

The scattering dynamics leading to the formation of Cl (2P(3/2)) and Cl* (2P(1/2)) products of the CH(3)+HCl reaction (at a mean collision energy =22.3 kcal mol(-1)) and the Cl (2P(3/2)) products of the CD(3)+HCl reaction (at =19.4 kcal mol(-1)) have been investigated by using photodissociation of CH(3)I and CD(3)I as sources of translationally hot methyl radicals and velocity map imaging of the Cl atom products. Image analysis with a Legendre moment fitting procedure demonstrates that, in all three reactions, the Cl/Cl* products are mostly forward scattered with respect to the HCl in the center-of-mass (c.m.) frame but with a backward scattered component. The distributions of the fraction of the available energy released as translation peak at f(t)=0.31-0.33 for all the reactions, with average values that lie in the range =0.42-0.47. The detailed analysis indicates the importance of collision energy in facilitating the nonadiabatic transitions that lead to Cl* production. The similarities between the c.m.-frame scattering and kinetic energy release distributions for Cl and Cl* channels suggest that the nonadiabatic transitions to a low-lying excited potential energy surface (PES) correlating to Cl* products occur after passage through the transition state region on the ground-state PES. Branching fractions for Cl* are determined to be 0.14+/-0.02 for the CH(3)+HCl reaction and 0.20+/-0.03 for the CD(3)+HCl reaction. The difference cannot be accounted for by changes in collision energy, mass effects, or vibrational excitation of the photolytically generated methyl radical reagents and instead suggests that the low-frequency bending modes of the CD(3)H or CH(4) coproduct are important mediators of the nonadiabatic couplings occurring in this reaction system.

Imaging the nonadiabatic dynamics of the CH3 + HCl reaction

LAB-frame velocity distributions of Cl-atoms produced in the photoinitiated reaction of CH(3) radicals with HCl have been measured for both the ground Cl ((2)P(3/2)) and excited Cl* ((2)P(1/2)) spin-orbit states using a DC slice velocity-map ion imaging technique. The similarity of these distributions, as well as the average internal excitation of methane co-products for both Cl and Cl* pathways, suggest that all the reactive flux proceeds through the same transition state on the ground potential energy surface (PES) and that the couplings which promote nonadiabatic transitions to the excited PES correlating to Cl* occur later in the exit channel, beyond the TS region. The nature of these couplings is discussed in light of initial vibrational excitation of CH(3) radicals as well as previously reported nonadiabatic reactivity in other polyatomic molecule reactions. Furthermore, the scattering of the reaction products, derived using the photoloc method, suggests that at the high collision energy of our experiment (E(coll) = 22.3 kcal mol(-1)), large impact parameter collisions are favoured with a reduced kinematic constraint on the internal excitation of the methane co-product.

Nonadiabatic dynamics in the CH3+HCl→CH4+Cl(PJ2) reaction

Nonadiabatic dynamics in the title reaction have been investigated by 2+1 REMPI detection of the Cl({sup 2}P{sub 3/2}) and Cl{sup *}({sup 2}P{sub 1/2}) products. Reaction was initiated by photodissociation of CH{sub 3}I at 266 nm within a single expansion of a dilute mixture of CH{sub 3}I and HCl in argon, giving a mean collision energy of 7800 cm{sup -1} in the center-of-mass frame. Significant production of Cl* was observed, with careful checks made to ensure that no additional photochemical or inelastic scattering sources of Cl* perturbed the measurements. The fraction of the total yield of Cl({sup 2}P{sub J}) atoms formed in the J=(1/2) level at this collision energy was 0.150{+-}0.024, and must arise from nonadiabatic dynamics because the ground potential energy surface correlates to CH{sub 4}+Cl({sup 2}P{sub 3/2}) products.Nonadiabatic dynamics in the title reaction have been investigated by 2+1 REMPI detection of the Cl(2P(3/2)) and Cl*(2P(1/2)) products. Reaction was initiated by photodissociation of CH(3)I at 266 nm within a single expansion of a dilute mixture of CH(3)I and HCl in argon, giving a mean collision energy of 7800 cm(-1) in the center-of-mass frame. Significant production of Cl* was observed, with careful checks made to ensure that no additional photochemical or inelastic scattering sources of Cl* perturbed the measurements. The fraction of the total yield of Cl(2P(J)) atoms formed in the J=1/2 level at this collision energy was 0.150+/-0.024, and must arise from nonadiabatic dynamics because the ground potential energy surface correlates to CH(4)+Cl(2P(3/2)) products.

Nonadiabatic dynamics in the CH{sub 3}+HCl{yields}CH{sub 4}+Cl({sup 2}P{sub J}) reaction

Nonadiabatic dynamics in the title reaction have been investigated by 2+1 REMPI detection of the Cl({sup 2}P{sub 3/2}) and Cl{sup *}({sup 2}P{sub 1/2}) products. Reaction was initiated by photodissociation of CH{sub 3}I at 266 nm within a single expansion of a dilute mixture of CH{sub 3}I and HCl in argon, giving a mean collision energy of 7800 cm{sup -1} in the center-of-mass frame. Significant production of Cl* was observed, with careful checks made to ensure that no additional photochemical or inelastic scattering sources of Cl* perturbed the measurements. The fraction of the total yield of Cl({sup 2}P{sub J}) atoms formed in the J=(1/2) level at this collision energy was 0.150{+-}0.024, and must arise from nonadiabatic dynamics because the ground potential energy surface correlates to CH{sub 4}+Cl({sup 2}P{sub 3/2}) products.Nonadiabatic dynamics in the title reaction have been investigated by 2+1 REMPI detection of the Cl(2P(3/2)) and Cl*(2P(1/2)) products. Reaction was initiated by photodissociation of CH(3)I at 266 nm within a single expansion of a dilute mixture of CH(3)I and HCl in argon, giving a mean collision energy of 7800 cm(-1) in the center-of-mass frame. Significant production of Cl* was observed, with careful checks made to ensure that no additional photochemical or inelastic scattering sources of Cl* perturbed the measurements. The fraction of the total yield of Cl(2P(J)) atoms formed in the J=1/2 level at this collision energy was 0.150+/-0.024, and must arise from nonadiabatic dynamics because the ground potential energy surface correlates to CH(4)+Cl(2P(3/2)) products.

Non-adiabatic dynamics in the CH 3 + HCl → CH 4 + Cl( 2 P J ) reaction

Nonadiabatic dynamics in the title reaction have been investigated by 2+1 REMPI detection of the Cl({sup 2}P{sub 3/2}) and Cl{sup *}({sup 2}P{sub 1/2}) products. Reaction was initiated by photodissociation of CH{sub 3}I at 266 nm within a single expansion of a dilute mixture of CH{sub 3}I and HCl in argon, giving a mean collision energy of 7800 cm{sup -1} in the center-of-mass frame. Significant production of Cl* was observed, with careful checks made to ensure that no additional photochemical or inelastic scattering sources of Cl* perturbed the measurements. The fraction of the total yield of Cl({sup 2}P{sub J}) atoms formed in the J=(1/2) level at this collision energy was 0.150{+-}0.024, and must arise from nonadiabatic dynamics because the ground potential energy surface correlates to CH{sub 4}+Cl({sup 2}P{sub 3/2}) products.Nonadiabatic dynamics in the title reaction have been investigated by 2+1 REMPI detection of the Cl(2P(3/2)) and Cl*(2P(1/2)) products. Reaction was initiated by photodissociation of CH(3)I at 266 nm within a single expansion of a dilute mixture of CH(3)I and HCl in argon, giving a mean collision energy of 7800 cm(-1) in the center-of-mass frame. Significant production of Cl* was observed, with careful checks made to ensure that no additional photochemical or inelastic scattering sources of Cl* perturbed the measurements. The fraction of the total yield of Cl(2P(J)) atoms formed in the J=1/2 level at this collision energy was 0.150+/-0.024, and must arise from nonadiabatic dynamics because the ground potential energy surface correlates to CH(4)+Cl(2P(3/2)) products.