TY - JOUR

T1 - Self-assembling of the neutral intermediate with chemically bound argon in photoexcited van der Waals complex Ar-I2

AU - Bogomolov, Alexandr S.

AU - Dozmorov, Nikolay V.

AU - Kochubei, Sergei A.

AU - Baklanov, Alexey V.

N1 - Funding Information: The reported study was funded by the Russian Foundation for Basic Research under Project No. 20-32-70065. The authors gratefully acknowledge the very useful discussion on the electronic structure of the high-lying electronic states in the system argon–iodine with Dr. Apostolos Kalemos. The authors have no conflicts to disclose. Publisher Copyright: © 2021 Author(s).

PY - 2021/9/28

Y1 - 2021/9/28

N2 - Photodissociation of the van der Waals complex Ar-I2 after excitation into the Rydberg states of I2 has been investigated with velocity map imaging of photofragments. Formation of the translationally hot ions of argon Ar+ with three modes in kinetic energy distribution has been revealed. The measured dependence of the kinetic energy of Ar+ on the pumping photon energy indicates the appearance of Ar+ from three channels of the photodissociation of the linear intermediate Ar+-I-I− containing chemically bound argon. These channels are (1) dissociation into Ar++ I2−; (2) three-body dissociation into (Ar+)* + I* + I−, with (Ar+)* and I* being the 2P1/2 states of the species; and (3) two-body electron photodetachment, giving rise to Ar+ + I2 + e. Three indicated channels are similar to those established for the photodissociation of trihalide anions. This similarity confirms the conclusion on the formation of the Ar+-I-I− intermediate, which is isoelectronic to the trihalide anion Cl-I-I−. The mechanism of the Ar+-I-I− formation involves two-photon excitation of the complex Ar-I2 into the Rydberg state of I2 converted into the ion-pair state and further electron transfer from Ar to I+ of the ion-pair state. The self-assembling of the structure making the formation of the Ar+-I-I− intermediate energetically accessible is confirmed by modeling the dynamics in the excited linear complex Ar-I2. Photoexcitation of the van der Waals complexes of noble gases with halogens into the ion-pair states of halogen is supposed to be a promising approach for generating the new chemical compounds of noble gas atoms.

AB - Photodissociation of the van der Waals complex Ar-I2 after excitation into the Rydberg states of I2 has been investigated with velocity map imaging of photofragments. Formation of the translationally hot ions of argon Ar+ with three modes in kinetic energy distribution has been revealed. The measured dependence of the kinetic energy of Ar+ on the pumping photon energy indicates the appearance of Ar+ from three channels of the photodissociation of the linear intermediate Ar+-I-I− containing chemically bound argon. These channels are (1) dissociation into Ar++ I2−; (2) three-body dissociation into (Ar+)* + I* + I−, with (Ar+)* and I* being the 2P1/2 states of the species; and (3) two-body electron photodetachment, giving rise to Ar+ + I2 + e. Three indicated channels are similar to those established for the photodissociation of trihalide anions. This similarity confirms the conclusion on the formation of the Ar+-I-I− intermediate, which is isoelectronic to the trihalide anion Cl-I-I−. The mechanism of the Ar+-I-I− formation involves two-photon excitation of the complex Ar-I2 into the Rydberg state of I2 converted into the ion-pair state and further electron transfer from Ar to I+ of the ion-pair state. The self-assembling of the structure making the formation of the Ar+-I-I− intermediate energetically accessible is confirmed by modeling the dynamics in the excited linear complex Ar-I2. Photoexcitation of the van der Waals complexes of noble gases with halogens into the ion-pair states of halogen is supposed to be a promising approach for generating the new chemical compounds of noble gas atoms.

UR - http://www.scopus.com/inward/record.url?scp=85116125200&partnerID=8YFLogxK

U2 - 10.1063/5.0059414

DO - 10.1063/5.0059414

M3 - Article

C2 - 34598590

AN - SCOPUS:85116125200

VL - 155

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 12

M1 - 124308

ER -