High-lying Rydberg states and ionization energy of vinyl chloride studied by two-photon resonant ionization spectroscopy

Chang, Jia‐Lin; Shieh, Jau-Chin; Wu, Jin-Ming; Li, Runhua; Chen, Yit‐Tsong

doi:10.1016/s0009-2614(00)00707-7

Cited by 17 publications

(5 citation statements)

References 26 publications

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“…The ionization energy determined from its position after corrections for the electric field present inside the source is 10.0062 ± 0.0006 eV for C 2 H 3 35 Cl + . This is compared with previous measurements − in Table . The ionization energy to the Ã state of the cation is also listed.…”

Section: Resultsmentioning

confidence: 72%

Vibrational Spectroscopy and State-Specific Dissociation Dynamics for Vinyl Chloride Cation in the B̃ State

Lee

Kim

2007

J. Phys. Chem. A

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C(2)H(3)(35)Cl+ in the ground vibronic state was generated by one-photon mass-analyzed threshold ionization spectrometry, and its photodissociation in the 461-406 nm range was investigated. Ionization energy to the ground state of C(2)H(3)(35)Cl+ was 10.0062 +/- 0.0006 eV while its B state onset was higher by 2.7456 +/- 0.0003 eV. A vibrational spectrum of the cation in the B state obtained by recording the product ion yield as a function of wavelength was analyzed by referring to the quantum chemical results at the TDDFT/B3LYP/6-311++(df,pd) level. Analysis of product time-of-flight profiles recorded with different laser polarization angles showed that the dissociation pathway for the cation in the B state changed with the vibrational energy, from internal conversion to X and statistical dissociation therein to curve crossing to C and repulsive dissociation therein. B --> C curve crossing seemed to occur along a direction close to the C-Cl bond stretch.

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Section: Resultsmentioning

confidence: 72%

Vibrational Spectroscopy and State-Specific Dissociation Dynamics for Vinyl Chloride Cation in the B̃ State

Lee

Kim

2007

J. Phys. Chem. A

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“…It is therefore expected that the parameter of the geometrical structure related to this delocalized π bond will be changed upon ionization. The calculated geometrical structures of vinyl chloride and its cation have been reported. , Figure shows the calculated results at the level of RMP2/6-311++g(3df,3dp) using the MOLPRO software package . It is seen that the ionization does not greatly change the geometrical structure, and the 0° transition band in the ZEKE spectrum is expected to be the strongest one.…”

Section: Resultsmentioning

confidence: 99%

“…The photoionization efficiency spectroscopy (PI), PES, and TPES methods have been used to determine its IE. − Recently, the energy levels of the Rydberg series for CH 2 CHCl have been measured by two-photon RMEPI and also VUV photon-absorption spectroscopic methods. The IE has been thus determined by extrapolation of the Rydberg series. , The reported IE values from PI, PES, and TPES measurements have uncertainties usually larger than 0.01 eV (80 cm -1 ), − and the reported data from extrapolation of the Rydberg series has an uncertainty of 6 cm -1 …”

Section: Introductionmentioning

confidence: 99%

Vibrational Structure of Vinyl Chloride Cation Studied by Using One-Photon Zero-Kinetic Energy Photoelectron Spectroscopy

Zhang

2007

J. Phys. Chem. A

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The vibrational structure of vinyl chloride cation, CH(2)CHCl+ (X(2)A' '), has been studied by vacuum ultraviolet (VUV) zero-kinetic energy (ZEKE) photoelectron spectroscopy. Among nine symmetric vibrational modes, the fundamental frequencies of six modes have been determined. The first overtone of the out-of-plane CH(2) twist vibrational mode has been also measured. In addition to these, the combination and overtone bands of the above vibrational modes about 4500 cm(-1) above the ground state have been observed in the ZEKE spectrum. The vibrational band intensities of the ZEKE spectrum can be described approximately by the Franck-Condon factors with harmonic approximation. The ZEKE spectrum has been assigned based on the harmonic frequencies and Franck-Condon factors from theoretical calculations. The ionization energy (IE) of CH(2)CHCl is determined as 80705.5 +/- 2.5 (cm(-1)) or 10.0062 +/- 0.0003 (eV).

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“…It is already known ,− that the X, A, B, and C states of the C 2 H 3 Cl + ion are 1 2 A‘ ‘, 1 2 A‘, 2 2 A‘ ‘, and 2 2 A‘, respectively. Experimental vertical ionization energies (VIEs) for the four states of C 2 H 3 Cl + were already reported by many groups. −,− On the basis of the experimental VIE values for different states of the ion, relative energy values (denoted by T v ‘ in the present paper) of the excited states to the ground state of the ion at the ground-state geometry of the neutral molecule can be evaluated. Using the experimental VIE values for the X, A, B, and C states (10.18, 11.72, 13.14, and 13.56 eV, respectively) reported by Lake and Thompson, the T v ‘ values for the 1 2 A‘, 2 2 A‘ ‘, and 2 2 A‘ states are evaluated to be 1.54, 2.96, and 3.38 eV, respectively.…”

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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High-lying Rydberg states and ionization energy of vinyl chloride studied by two-photon resonant ionization spectroscopy

Cited by 17 publications

References 26 publications

Vibrational Spectroscopy and State-Specific Dissociation Dynamics for Vinyl Chloride Cation in the B̃ State

Vibrational Spectroscopy and State-Specific Dissociation Dynamics for Vinyl Chloride Cation in the B̃ State

Vibrational Structure of Vinyl Chloride Cation Studied by Using One-Photon Zero-Kinetic Energy Photoelectron Spectroscopy

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

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High-lying Rydberg states and ionization energy of vinyl chloride studied by two-photon resonant ionization spectroscopy

Cited by 17 publications

References 26 publications

Vibrational Spectroscopy and State-Specific Dissociation Dynamics for Vinyl Chloride Cation in the B̃ State

Vibrational Spectroscopy and State-Specific Dissociation Dynamics for Vinyl Chloride Cation in the B̃ State

Vibrational Structure of Vinyl Chloride Cation Studied by Using One-Photon Zero-Kinetic Energy Photoelectron Spectroscopy

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

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