Stretching-mode specificity in the Cl + CH3D(v(1)-I, v(1)-II, and v(4)=1; |jK) reactions: dependency on the initial |jK selectivity

Mondal, Sohidul1; Pan, Huilin1,2; Liu, Kopin1,3,4

2022-09-01

10.1039/d2cp03614b

PHYSICAL CHEMISTRY CHEMICAL PHYSICS   Impact Factor & Quartile

1463-9076

1463-9084

The title reactions were studied at a collisional energy of 5.4 kcal mol(-1) in a crossed-beam product-imaging experiment. The dynamics attributes of the dominant ground-state CH2D(0(0)) and the accompanied C-D bend-excited CH2D(6(1)) products were imaged in reactions with totally 16 ro-vibrationally selected states of the CH3D(v(i), |jK) reagents. We found that all three vibrational excitations yielded marked |jK-dependent rate-enhancements in forming the (0(0), 0/1)(s) product pairs. Furthermore, for a given rotational |jK-mode, a vibrational-mode propensity of v(4) > v(1)-I > v(1)-II in rate promotion and a clear manifestation of the Fermi-phase-induced interference effect of the latter two were observed. Compared to the reactivity of the rotationless state |jK = |00, a minute rotational-excitation of all three stretch-excited CH3D(v(i) = 1) reagents could yield significantly higher reaction rates for the product pair (0(0), 0)(s), but not so for (0(0), 1)(s). The signals in forming the (6(1), 0)(s) pair were clearly notable but smaller than that of the ground-state reaction product pair, (0(0), 0)(g). An opposite propensity of v(1)-II approximate to v(1)-I > v(4) with a milder dependency on the initial |jK-states was observed. The angular distributions of the (0(0), 0)(s) pairs were nearly identical for all ro-vibrationally excited reagents, displaying the typical trait for a direct abstraction of the rebound mechanism. Similar distributions were found for the (6(1), 0)(s) pairs; yet, both pairs deviated substantially from the peripheral feature of the ground-state reaction pair of (0(0), 0)(g). Those of the (0(0), 1)(s) pairs in reactions with v(4)-excitation featured a prominent forward-peaking distribution-suggestive of a time-delayed, resonance-mediated pathway, again with little dependency on the initial |jK-states. As for the reactions with the two Fermi-dyads, v(1)-I and v(1)-II, albeit showing globally similar distributions to that for v(4), a substantial variation with the initial rotational-mode excitation could be discerned in the forward-peaking features. To unravel the impact of the Fermi-phase on the |jK-dependent attributes, we adopted a comparative approach by contrasting the observations in reactions with the Fermi-dyad reagents (the superposition states) to those with the pure-state reagents. Remarkable distinctions are unveiled and elucidated with the unexplained results explicitly pointed out, which call for future theoretical investigations for deeper understanding.

SCI

English

Others

Ministry of Science and Technology of Taiwan[MOST-105-2113-M-001-019] ; Academia Sinica[2318-1030200] ; National Natural Science Foundation of China[22003024] ; Guangdong Introduced Innovative RD Team Project[2019ZT08L455] ; State Key Laboratory of Molecular Reaction Dynamics[SKLMRD-K202119]

Chemistry ; Physics

Chemistry, Physical ; Physics, Atomic, Molecular & Chemical

WOS:000860904000001

ROYAL SOC CHEMISTRY

CHEMISTRY

Web of Science

1.Acad Sinica, Inst Atom & Mol Sci IAMS, POB 23-166, Taipei 10699, Taiwan
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
3.Natl Sun Yat Sen Univ, Aerosol Sci Res Ctr, Kaohsiung 80424, Taiwan
4.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China

Mondal, Sohidul,Pan, Huilin,Liu, Kopin. Stretching-mode specificity in the Cl + CH3D(v(1)-I, v(1)-II, and v(4)=1; |jK) reactions: dependency on the initial |jK selectivity[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2022.

Mondal, Sohidul,Pan, Huilin,&Liu, Kopin.(2022).Stretching-mode specificity in the Cl + CH3D(v(1)-I, v(1)-II, and v(4)=1; |jK) reactions: dependency on the initial |jK selectivity.PHYSICAL CHEMISTRY CHEMICAL PHYSICS.

Mondal, Sohidul,et al."Stretching-mode specificity in the Cl + CH3D(v(1)-I, v(1)-II, and v(4)=1; |jK) reactions: dependency on the initial |jK selectivity".PHYSICAL CHEMISTRY CHEMICAL PHYSICS (2022).