Dissociation dynamics of 3-and 4-nitrotoluene radical cations: Coherently driven C-NO2 bond homolysis

被引:16
|
作者
Boateng, Derrick Ampadu [1 ]
Gutsev, Gennady L. [2 ]
Jena, Puru [3 ]
Tibbetts, Katharine Moore [1 ]
机构
[1] Virginia Commonwealth Univ, Dept Chem, Richmond, VA 23284 USA
[2] Florida A&M Univ, Dept Phys, Tallahassee, FL 32307 USA
[3] Virginia Commonwealth Univ, Dept Phys, Richmond, VA 23284 USA
来源
JOURNAL OF CHEMICAL PHYSICS | 2018年 / 148卷 / 13期
关键词
ULTRAFAST PHOTODISSOCIATION DYNAMICS; NONADIABATIC MULTIELECTRON DYNAMICS; EXCITED ELECTRONIC STATES; FIELD MASS-SPECTROMETRY; 1.4; MU-M; FEMTOSECOND LASER; ENERGETIC MATERIALS; POLYATOMIC-MOLECULES; AB-INITIO; FRAGMENTATION;
D O I
10.1063/1.5024892
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Monosubstituted nitrotoluenes serve as important model compounds for nitroaromatic energetic molecules such as trinitrotoluene. This work investigates the ultrafast nuclear dynamics of 3- and 4-nitrotoluene radical cations using femtosecond pump-probe measurements and the results of density functional theory calculations. Strong-field adiabatic ionization of 3- and 4-nitrotoluene using 1500 nm, 18 fs pulses produces radical cations in the ground electronic state with distinct coherent vibrational excitations. In both nitrotoluene isomers, a one-photon excitation with the probe pulse results in NO2 loss to form C7H7+, which exhibits out-of-phase oscillations in yield with the parent molecular ion. The oscillations in 4-nitrotoluene with a period of 470 fs are attributed to the torsional motion of the NO2 group based on theoretical results showing that the dominant relaxation pathway in 4-nitrotoluene radical cations involves the rotation of the NO2 group away from the planar geometry. The distinctly faster oscillation period of 216 fs in 3-nitrotoluene is attributed to an in-plane bending motion of the NO2 and CH3 moieties based on analysis of the normal modes. These results demonstrate that coherent nuclear motions determine the probability of C-NO2 homolysis in the nitrotoluene radical cations upon optical excitation within several hundred femtoseconds of the initial ionization event. Published by AIP Publishing.
引用
收藏
页数:10
相关论文
共 50 条
  • [31] THERMOCHEMISTRY AND DISSOCIATION DYNAMICS OF STATE-SELECTED C4H8O2+ IONS .3. ETHYL-ACETATE
    FRASERMONTEIRO, L
    FRASERMONTEIRO, ML
    BUTLER, JJ
    BAER, T
    JOURNAL OF PHYSICAL CHEMISTRY, 1982, 86 (05): : 752 - 757
  • [32] PHOTOBROMINATION OF C2H5CL IN THE PRESENCE OF C2H6 - THE HEAT OF FORMATION OF THE CH3CHCL RADICAL AND THE D-DEGREES-(CH3CHCL-H) BOND-DISSOCIATION ENERGY
    TSCHUIKOWROUX, E
    SALOMON, DR
    JOURNAL OF PHYSICAL CHEMISTRY, 1987, 91 (03): : 699 - 702
  • [33] THE CALCULATED STRUCTURES OF THE C4H8NO+ CATIONS RESULTING FROM THE UNIMOLECULAR GAS-PHASE DISSOCIATION (CH3)2NCOCH2X.+-]C4H8NO++X.(X=CL,NO2)
    FRENKING, G
    SCHWARZ, H
    JOURNAL OF COMPUTATIONAL CHEMISTRY, 1982, 3 (02) : 251 - 259
  • [34] STRUCTURES OF DECOMPOSING AND NON-DECOMPOSING GAS-PHASE [C4H6O]+. RADICAL CATIONS, AND THEIR [C2H2O]+. AND [C3H6]+. PRODUCT IONS
    DASS, C
    GROSS, ML
    ORGANIC MASS SPECTROMETRY, 1990, 25 (01): : 24 - 32
  • [35] DYNAMICS OF MULTIPHOTON IONIZATION DISSOCIATION OF 2,4-HEXADIYNE BY THE 2-COLOR PICOSECOND PUMP PUMP MASS-SPECTROMETRIC TECHNIQUE - FORMATION OF C6H5+, C4H4+, AND C4H3+ IONS
    GOBELI, DA
    SIMON, JD
    ELSAYED, MA
    JOURNAL OF PHYSICAL CHEMISTRY, 1984, 88 (18): : 3949 - 3951
  • [36] Superoxide (•O2-) radical species driven type II TiO2/g-C3N4 heterojunction photocatalyst for RhB dye degradation
    Yadav, Smita M.
    Desai, Mangesh A.
    Sartale, Shrikrishna D.
    JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 2023, 34 (22)
  • [37] Superoxide (•O2−) radical species driven type II TiO2/g-C3N4 heterojunction photocatalyst for RhB dye degradation
    Smita M. Yadav
    Mangesh A. Desai
    Shrikrishna D. Sartale
    Journal of Materials Science: Materials in Electronics, 2023, 34
  • [38] Charge Carrier Dynamics of CsPbBr3/g-C3N4 Nanoheterostructures in Visible-Light-Driven CO2-to-CO Conversion
    Chen, Yu-Hung
    Tsai, Kai-An
    Liu, Tzu-Wei
    Chang, Yao-Jen
    Wei, Yu-Chen
    Zheng, Meng-Wei
    Liu, Shou-Heng
    Liao, Mei-Yi
    Sie, Pei-Yu
    Lin, Jarrn-Horng
    Tseng, Shih-Wen
    Pu, Ying-Chih
    JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2023, 14 (01): : 122 - 131
  • [39] ELECTROCHEMICAL OXIDATION OF [1.1.1.1]PAGODANES, BISSECODODECAHEDRA(DI)ENES, SECODODECAHEDRA(DI)ENES AND DODECAHEDRA(DI)ENES - STABILITY OF CAGED 4C/3E RADICAL CATIONS AND 4C/2E DICATIONS
    WEBER, K
    LUTZ, G
    KNOTHE, L
    MORTENSEN, J
    HEINZE, J
    PRINZBACH, H
    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1995, (11): : 1991 - 1997
  • [40] Visible light-driven selective cleavage of Cα-Cβ or Cβ-O bond in lignin β-O-4 model into high-value aromatic chemicals over surface modified 2D g-C3N4
    Tan, Hongzi
    Zhang, Pengrui
    Geng, Xuele
    Zhang, Wenhao
    Song, Feng
    Zhao, Rongrong
    Zhang, Keqin
    Cui, Hongyou
    Chen, Xuxing
    Zou, Jian-Ping
    SEPARATION AND PURIFICATION TECHNOLOGY, 2025, 354