A method is devised better to resolve the subbands of the ground vibronic band in the mass-analyzed threshold ionization (MATI) spectrum of CD(3)I. By selective photodissociation of CD(3)I(+) in these subbands, high-resolution spectra for the A(2)A(1)<--X(2)E(3/2) transition are recorded. Spectral analysis confirms our previous suggestion that these subbands are due to cations in different rotational K states; this demonstrates the capability of MATI to generate rovibronically selected ion beams. By using the rotational constants of CH(3)I(+) and CD(3)I(+) obtained by spectral analysis, the zero-point-level geometries of the cations in the X(2)E(3/2) and A(2)A(1) states are determined. To the best of our knowledge, this is the first time that the capability of MATI-PD to determine the geometry of a gas-phase polyatomic cation in an excited electronic state is demonstrated.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/cphc.200800207 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Impact of chlorine substitution on valence orbitals and ionization dynamics in 3-chloropyridine: Insights from high-resolution vacuum ultraviolet mass-analyzed threshold ionization study.
J Chem Phys
November 2024
Department of Chemistry and Institute for Molecular Science and Fusion Technology, Kangwon National University, Chuncheon 24341, Republic of Korea.
In this study, the effects of chlorine substitution on the valence orbitals and electronic states of 3-chloropyridine (3-CP) were investigated utilizing high-resolution vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy and computational methods. High-quality vibrational spectra were obtained from the VUV-MATI spectra of 3-CP isotopomers (35Cl and 37Cl), revealing high-quality vibrational spectra for the lowest cationic states. The adiabatic ionization energies (AIEs) of these isotopomers were accurately determined, providing detailed information about the electronic structure and ionization dynamics.
View Article and Find Full Text PDFAn Exhaustive Quantum-Classical Study of CF Using the Newly Formulated Parallel TDDVR Method.
J Phys Chem A
July 2024
Department of Chemistry, Bhatter College, Dantan, P.O. Dantan, Paschim Medinipur, Pin 721426, India.
We recently implemented our parallelized quantum-classical dynamical approach, known as the Time-Dependent Discrete Variable Representation (TDDVR) method, which is applied to the spectroscopically important hexafluorobenzene (HFBz) radical cation, where several conical intersections exist in their seven lowest excited electronic states (SB, SE, SB, SE, and SA) considering degeneracy among potential energy surfaces (PESs), to demonstrate their various dynamical aspects. This new parallel version shows almost linear scalability with increasing number of computing processors. To get photoelectron (PE) spectra, Mass-Analyzed Threshold Ionization (MATI) spectra, population dynamics, and many other dynamical observables, the first-principles dynamics is applied at the state-of-the-art level to the corresponding Hamiltonian, where the Jahn-Teller (JT) and pseudo-Jahn-Teller (PJT) type interactions are involved in those coupled seven electronic states.
View Article and Find Full Text PDFDeciphering the conformational preference and ionization dynamics of tetrahydrofuran: Insights from advanced spectroscopic techniques.
J Chem Phys
March 2024
Department of Chemistry and Institute for Molecular Science and Fusion Technology, Kangwon National University, Chuncheon 24341, Republic of Korea.
Tetrahydrofuran (THF) has garnered significant attention due to its pivotal role in biological and chemical processes. The diverse array of conformations exhibited by THF profoundly impacts its reactivity and interactions with other molecules. Understanding these conformational preferences is crucial for comprehending its molecular behavior.
View Article and Find Full Text PDFSpin-orbit coupling of electrons on separate lanthanide atoms of Pr2O2 and its singly charged cation.
J Chem Phys
December 2023
Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055, USA.
Although it plays a critical role in the photophysics and catalysis of lanthanides, spin-orbit coupling of electrons on individual lanthanide atoms in small clusters is not well understood. The major objective of this work is to probe such coupling of the praseodymium (Pr) 4f and 6s electrons in Pr2O2 and Pr2O2+. The approach combines mass-analyzed threshold ionization spectroscopy and spin-orbit multiconfiguration second-order quasi-degenerate perturbation theory.
View Article and Find Full Text PDFEffect of a single methyl substituent on the electronic structure of cobaltocene studied by computationally assisted MATI spectroscopy.
Phys Chem Chem Phys
January 2024
Institute of Atomic and Molecular Sciences, Academia Sinica, 1 Section 4, Roosevelt Road, Taipei, 10617, Taiwan.
Metallocenes represent archetypical organometallic compounds playing key roles in various fields of fundamental and applied chemistry. Many of their unique properties arise from low ionization energies (IE) which can be tuned by introducing substituents into the rings. Here we report the first mass-analyzed threshold ionization (MATI) spectrum of a methylmetallocene, (Cp')(Cp)Co (Cp' = η-CHMe, Cp = η-CH).
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!