Photodissociation spectroscopy of Ca+–CO2

Abstract

Electronic spectra are observed for the metal cation complex Ca+–CO2, using resonance-enhanced photodissociation spectroscopy. The complexes are produced in a laser vaporization/supersonic expansion source, size selected and excited on resonance, and the mass-analyzed product is measured in a time-of-flight mass spectrometer. Both Ca+ and CaO+ dissociation channels are observed to have sharp resonances. Spectra from two isotopomers, the 40Ca+ and 44Ca+ species, are recorded and analyzed. Transitions from the X 2Σ+(v″=0) ground vibronic state to several vibrational levels in the D 2Πr excited electronic state are measured. The structure of the complex is confirmed to be linear by the presence of prominent spin–orbit multiplets. Spectroscopic constants for the 40Ca+–CO2 complex are determined: ν00=22 099.1 cm−1, Aso′=136.3 cm−1, ωe′=258.9 cm−1, and ωexe′=4.23 cm−1.

The metal coordination in Ni+(CO2)n and NiO2+(CO2)m complexes

“…The wavelength dependence of the photodissociation yield makes it possible to obtain infrared resonance enhanced photodissociation spectroscopy for these clusters, as we have described previously for other metal cation complexes [20][21][22][23][24][25][26]. Fig.…”

“…Pure expansions in CO 2 or argon seeded with a small percent of CO 2 or oxygen are employed. Ions are mass-selected before IR laser excitation and fragment ions are mass analyzed afterwards with a specially designed reflectron time-of-flight spectrometer [20][21][22][23][24][25][26]. Infrared excitation in the CO 2 asymmetric stretch region is accomplished with a LaserVision optical parametric oscillator/amplifier system (OPO/OPA) pumped by an injection-seeded Continuum 9010 Nd:YAG laser.…”

“…Previous electronic spectroscopy studies have focused on the details of the structures and binding that occur when a single Chemical Physics Letters 380 (2003) 230-236 www.elsevier.com/locate/cplett CO 2 molecule binds to a metal cation. Brucat and coworkers [15,18,19] have studied several transition metal cation electronic spectra, while our group has investigated the main group cations Mg þ [20] and Ca þ [21]. In more recent work, we have studied the infrared resonance-enhanced photodissociation (IR-REPD) spectroscopy of M þ (CO 2 ) n complexes (M ¼ Fe, Mg, Al) by excitation near the CO 2 asymmetric stretch [22][23][24].…”

Photodissociation spectroscopy of the Ca+–N2 complex

“…Mass spectrometric techniques have produced abundant thermochemical data for metal ion-molecular complexes. [1][2][3] More recently, ab initio calculations [4][5][6][7][8][9] and optical spectroscopy studies [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27]30 have become the focus for studying metal ion-ligand interactions. Our research group has an ongoing program in the investigation of metal ion interactions in weakly bound complexes through mass-selected photodissociation spectroscopy.…”

Photo-induced reactions in the ion–molecule complex Mg+–OCNC2H5

“…[2][3][4][5][6][7][8] It is also a useful method to explore the dynamics of half-collision bimolecular reactions. [9][10][11][12][13][14][15][16][17][18][19][20][21] Singly charged alkaline earth metal cations have an open-shell structure and are iso-electronic to the alkali metal atoms. They have substantial oscillator strengths in the ultraviolet spectral regions, which can be easily accessed by pulsed laser sources.…”