Experimental and theoretical studies of the photoionization and dissociative photoionizations of vinyl chloride

Sheng, Liusi; Qi, Fei; Li, Tao; Zhang, Yunwu; Yu, Shulin; Wong, Chun Kit; Li, Wai‐Kee

doi:10.1016/0168-1176(95)04263-k

Cited by 32 publications

(37 citation statements)

References 25 publications

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“…Recently, we have analyzed the 2ϩ1 resonanceenhanced multiphoton ionization ͑REMPI͒ spectra of VC in the energy region of 7.3-10 eV, from which the adiabatic ionization energy ͑AIE͒ of VC is determined to be 80 720Ϯ6 cm Ϫ1 ͑10.0080Ϯ0.0007 eV͒, 29,30 in agreement with that obtained by photoelectron spectroscopy. [31][32][33][34][35][36] Our work, in conjunction with a previous REMPI study on VC by Williams and Cool, 37 provide valuable insights into the excited states involved in the photodissociation dynamics of VC at 7.3-10 eV. Below 7.3 eV, the absorption spectrum of VC reported by Berry 14 shows a broad and continuous band, yet with some weak features.…”

Section: Introductionmentioning

confidence: 60%

Ab initio calculations of low-lying electronic states of vinyl chloride

Chang¹,

Chen²

2002

The Journal of Chemical Physics

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The equilibrium geometries, vibrational frequencies, excitation energies, and oscillator strengths of vinyl chloride in the ground and five lowest-lying excited singlet states have been calculated using MP2, CIS, CASSCF, and MRCI methods with the 6-311ϩϩG** basis set. The geometries and vibrational frequencies of the ground and excited states are utilized to compute Franck-Condon factors. Calculated vibronic spectra for the transitions from the ground state to these five excited states are in agreement with experiment at 52 500-60 000 cm Ϫ1 , with major contributions from the Ã (1 1 AЉ)←X (1 1 AЈ) and C (2 1 AЈ)←X (1 1 AЈ) transitions. In this study, two spin-forbidden transitions of b (1 3 AЉ)←X (1 1 AЈ) and c (2 3 AЉ)←X (1 1 AЈ) are calculated to locate in 45 000-54 000 cm Ϫ1 , and could be responsible for the observed one-photon absorption spectrum due to an intensity borrowing caused by the spin-orbit coupling of the Cl atom. Based on calculation, we speculate that upon the excitation of vinyl chloride at 193 nm the b (1 3 AЉ) or c (2 3 AЉ) excited state, instead of the ͑,*͒, is initially prepared prior to the subsequent photodissociation processes.

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Section: Introductionmentioning

confidence: 60%

Ab initio calculations of low-lying electronic states of vinyl chloride

Chang¹,

Chen²

2002

The Journal of Chemical Physics

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“…[32][33][34][35][36] However, the ATcT vinyl cation enthalpy of formation is based predominantly on calculations as well as on dissociative photoionization thresholds for halogen loss from vinyl halogenides. [37][38][39] On the one hand, as we will show later, although increasingly accurate wave function approximation methods converge to the exact solution of the Schrödinger equation, 40 the optimized geometries and relative energies of the different vinyl cation isomers depend on the level of theory to a disconcerting degree. On the other, in the presence of reverse barriers, dissociative photoionization thresholds correspond to the transition state energy and not to the thermochemical threshold to halogen loss.…”

Section: Introductionmentioning

confidence: 98%

The ionization energy of the vinyl radical: a Mexican standoff with a happy ending

Zhou

Hemberger

et al. 2019

Phys. Chem. Chem. Phys.

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“…Photodissociation studies for the C 2 H 3 Cl + ion were carried out by several groups, 5,[11][12][13]17,18 and the observed products and the measured dissociation energies and appearance energies were reported.…”

Section: Introductionmentioning

confidence: 99%

Low-Lying Electronic States and Cl-Loss Photodissociation of the C₂H₃Cl⁺ Ion Studied Using Multiconfiguration Second-Order Perturbation Theory

2008

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We studied the 1(2)A' '(X2A' '), 1(2)A' (A2A'), 2(2)A' ' (B2A' '), and 2(2)A' (C2A') states of the C2H3Cl+ ion using the complete active space self-consistent field (CASSCF) and multiconfiguration second-order perturbation theory (CASPT2) methods. For the four ionic states, we calculated the equilibrium geometries, adiabatic (T0) and vertical (Tv) excitation energies, and relative energies (Tv') at the geometry of the molecule at the CASPT2 level and the Cl-loss dissociation potential energy curves (PECs) at the CASPT2//CASSCF level. The computed oscillator strength f value for the X2A' ' <-- A2A' transition is very small, which is in line with the experimental fact that the A state has a long lifetime. The CASPT2 geometry and T0 value for the A2A' state are in good agreement with experiment. The CASPT2 Tv' values for the A2A', B2A' ', and C2A' states are in good agreement with experiment. The Cl-loss PEC calculations predict that the X2A' ', A2A', and C2A' states correlate to C2H3+ (XA1) and the BA' ' state to C2H3+ (1A' ') (the B2A' ' and C2A' PECs cross at R(C-Cl) approximately 2.24 A). Our calculations indicate that at 357 nm the X2A' ' state can undergo a transition to B2A' ' followed by a predissociation of B2A' ' by the repulsive C2A' state (via the B/C crossing), leading to C2H3+ (X1A1), and therefore confirm the experimentally proposed pathway for the photodissociation of X2A' ' at 357 nm. Our CASPT2 D0 calculations support the experimental fact that the X state does not undergo dissociation in the visible spectral region and imply that a direct dissociation of the A state to C2H3+ (X1A1) is energetically feasible.

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Experimental and theoretical studies of the photoionization and dissociative photoionizations of vinyl chloride

Cited by 32 publications

References 25 publications

Ab initio calculations of low-lying electronic states of vinyl chloride

Ab initio calculations of low-lying electronic states of vinyl chloride

The ionization energy of the vinyl radical: a Mexican standoff with a happy ending

Low-Lying Electronic States and Cl-Loss Photodissociation of the C₂H₃Cl⁺ Ion Studied Using Multiconfiguration Second-Order Perturbation Theory

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Experimental and theoretical studies of the photoionization and dissociative photoionizations of vinyl chloride

Cited by 32 publications

References 25 publications

Ab initio calculations of low-lying electronic states of vinyl chloride

Ab initio calculations of low-lying electronic states of vinyl chloride

The ionization energy of the vinyl radical: a Mexican standoff with a happy ending

Low-Lying Electronic States and Cl-Loss Photodissociation of the C2H3Cl+ Ion Studied Using Multiconfiguration Second-Order Perturbation Theory

Contact Info

Product

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Low-Lying Electronic States and Cl-Loss Photodissociation of the C₂H₃Cl⁺ Ion Studied Using Multiconfiguration Second-Order Perturbation Theory